Herbicidal 2-aryl-1,2,4-triazine-3,5(2H,4H)-diones and sulfur analogs thereof

ABSTRACT

Herbicidal utility for 2-aryl-1,2,4-triazine-3,5(2H,4H)-diones and sulfur analogs is disclosed and exemplified. Many of the disclosed compounds are novel. Methods for preparing the herbicidal compounds and intermediates therefor are also disclosed.

This application is a continuation-in-part of application Ser. No.755,749, filed July 2, 1985, now abandoned.

The invention described in this application pertains to weed control inagriculture, horticulture, and other fields where there is a desire tocontrol unwanted plant growth. More specifically, the presentapplication describes herbicidal2-aryl-1,2,4-triazine-3,5(2H,4H)-diones, sulfur analogs thereof,compositions of them, methods of preparing them, and methods forpreventing or destroying undesired plant growth by preemergence orpostemergence application of the herbicidal compositions to the locuswhere control is desired. The present compounds may be used toeffectively control a variety of both grassy and broadleaf plantspecies. The present invention is particularly useful in agriculture, asa number of the compounds described herein show a selectivity favorableto soybean, corn, cotton, wheat, rice, or other crops at applicationlevels which prevent the growth of or destroy a variety of weeds.

1,2,4-Triazine-3,5(2H,4H)-diones as a class are generally associatedwith the pharmaceutical or animal health arts and are commonly referredto therein as 6-azauracils. Such compounds, however, are relativelyunknown in the herbicide art. In particular, there does not appear to beany disclosure of 2-aryltriazinediones in the art. Herbicidal activityis disclosed in German Offenlegungsschrift No. 3,016,304 for optionallysubstituted triazinediones having the formula ##STR1## where R¹ ishydrogen, hydroxymethyl or an ester derivative thereof such as a benzoicacid ester, optionally substituted aminomethyl, optionallyhalo-substituted 2-tetrahydrofuranyl, 2-(2H,5H)dihydrofuranyl, or2-tetrahydropyranyl, and R² is hydrogen, an optionally substitutedaminomethyl, optionally halo-substituted 2-tetrahydrofuranyl, or2-tetrahydropyranyl, with certain provisos.

European Published Patent Application No. 0 011 693 of 1979 refers tophenyltriazinediones having a --NHSO₂ CF₃ substituent on the phenylgroup. The compounds of the present invention do not require such asubstituent for their herbicidal effects.

It has now been discovered that 2-aryl-1,2,4-triazine-3,5-(2H,4H)-dionesand the corresponding sulfur analogs have herbicidal properties and maybe used effectively either preemergently or postemergently forherbicidal purposes.

The herbicidal compounds of this invention have the formula ##STR2##where Ar is an aryl radical, preferably a ring-substituted aryl radical.For instance it may have a benzene ring such as the radical indicated bythe following formula ##STR3## wherein X¹ may be for instance hydrogenor halogen, preferably fluorine or chlorine, the halogen atomadvantageously being positioned at the C-2 carbon atom of the phenylring;

X² may be hydrogen, halogen such as fluorine, chlorine, or bromine,alkyl of 1 to 6 (preferably 1 to 4) carbon atoms, particularly methyl,haloalkyl of 1 to 5 carbon atoms, for example, trifluoromethyl, alkoxyof 1 to 6 (preferably 1 to 4 ) carbon atoms, or phenoxy or phenylmethoxywhich may be ring substituted with halogen or alkyl or alkoxy of 1 to 4carbon atoms;

Z may be hydrogen or, preferably, a substituent or group selected fromfluorine, chlorine, bromine, iodine, cyano, nitro, amino,alkoxycarbonylamino of 1 to 6 (preferably 1 to 4) alkyl carbon atoms,di(alkylcarbonyl)amino in which each alkyl is of 1 to 6 (preferably 1 to4) carbon atoms, hydroxysulfonyl, alkyl of 1 to 6 (preferably 1 to 4)carbon atoms, haloalkyl of 1 to 5 carbon atoms, --QR, --CO--R⁶,--S(O)_(m) R⁸, --Q² R⁹, --OSO₂ R¹⁰, --NHN═CR¹¹ R¹², and --Q--CR³ R⁴--(CH₂)_(n) --CO--Q¹ --R⁵.

For Z=--QR, Q may be O, S, or NR⁷ ; R⁷ may be hydrogen or alkyl of 1 to6 (preferably 1 to 4) carbon atoms; and R may be alkyl of 1 to 6(preferably 1 to 4) carbon atoms, which may be substituted withcycloalkyl of 3 to 7 carbon atoms (for example, methyl, 1-methylethyl,or cyclohexylmethyl), cycloalkyl of 3 to 7 (preferably 5 or 6) carbonatoms which may be substituted with alkyl of 1 to 6 carbon atoms (forexample, cyclopentyl or methylcyclopropyl), alkoxyalkyl of 2 to 8(preferably 2 to 4) carbon atoms (for example, ethoxymethyl),alkoxyalkoxyalkyl of 3 to 8 (preferably 3 to 5) carbon atoms (forexample, 2-methoxyethoxymethyl), alkylthioalkyl of 2 to 8 (preferably 2to 4) carbon atoms or the sulfinyl or sulfonyl derivative thereof,tri(alkyl of 1 to 4 carbon atoms)silyl(alkyl of 1 to 4 carbon atoms)such as trimethylsilylmethyl, cyanoalkyl of 1 to 5 (preferably 1 to 3)alkyl carbon atoms such as cyanomethyl or 2-cyanoethyl, alkenyl of 2 to5 (preferably 3 to 5) carbon atoms such as 2-propenyl, alkynyl of 2 to 5(preferably 3 to 5) carbon atoms such as 2-propynyl, haloalkyl of 1 to 5(preferably 1 to 3) carbon atoms especially a fluoroalkyl, haloalkenylof 2 to 5 (preferably 3 to 5) carbon atoms, haloalkynyl of 2 to 5(preferably 3 to 5) carbon atoms such as 3-bromo-2-propynyl,alkylcarbonyl of 1 to 6 (preferably 1 to 4) alkyl carbon atoms such asacetyl, or dialkylaminocarbonyl or dialkylaminothiocarbonyl in whicheach alkyl is of 1 to 6 (preferably 1 to 4) carbon atoms.

The compounds in which Z=--QR, especially where X¹ is 2-F and X² is Clor Br, form a preferred embodiment of the invention; particularly whereQ is sulfur, more particularly where Q is oxygen. Frequently, R will beselected from among alkyl, cyanoalkyl, alkynyl, haloalkynyl, andalkoxyalkynyl. Typical such R groups include, for example,1-methylethyl, cyanomethyl, 2-propynyl, 3-bromo-2-propynyl, andmethoxymethyl. Preferably R will be 1-methylethyl or, especially,2-propynyl or methoxymethyl.

For Z=--CO--R⁶, R⁶ may be hydroxy, alkoxy or alkylthio of 1 to 6(preferably 1 to 4) carbon atoms such as methoxy or methylthio,alkoxyalkoxy of 2 to 6 (preferably 2 to 4) carbon atoms (for example,2-methoxyethoxy), amino, or alkylamino or dialkyamino wherein each alkylis of 1 to 6 (preferably 1 to 4) carbon atoms and may be substitutedwith alkoxy of 1 to 4 carbon atoms (for example, methylamino,dimethylamino, or methyl(2-methoxyethyl)amino). For example, Z, definedas --CO--R⁶, may be CO₂ H, CO₂ alkyl, CO--S-alkyl, CO₂ alkyl-O-alkyl,CONH₂, or CONH-alkyl or CON(alkyl)₂ in which any alkyl may besubstituted with alkoxy. Compounds in which Z is --CO--R⁶, especiallywhere X¹ is 2-F and X² is Cl or Br, form a preferred embodiment of theinvention.

For Z=--S(O)_(m) R⁸, m may be 1 or 2 and R⁸ may be alkyl of 1 to 6(preferably 1 to 4) carbon atoms or alkenyl or alkynyl of 2 to 5(preferably 3 to 5) carbon atoms. For example, Z may be --SO--CH₃, --SO₂CH(CH₃)₂, --SO₂ CH₂ CH═CH₂, or --SO--CH₂ C.tbd.CH.

For Z=--Q² R⁹, Q² may be sulfur or, preferably, oxygen, and R⁹ may be a5- or 6-membered ring heterocyclic group of 1 or 2 same or different(preferably the same) heteroatoms selected from O, S (including theS-oxide and S-dioxide), and N or an alkyl radical of 1 to 5 (preferably1 to 3) carbon atoms substituted with said heterocyclic group. R⁹ willfrequently be

(a) an optionally substituted and optionally benzene-adjoinednitrogen-containing heterocycle or an alkyl radical of 1 to 5 carbonatoms substituted with said heterocycle;

(b) an aromatic, optionally substituted and optionally benzene-adjoined,oxygen- or sulfur-containing heterocycle or an alkyl group of 1 to 5carbon atoms substituted therewith; or, advantageously,

(c) a non-aromatic, optionally substituted and optionallybenzene-adjoined, oxygen- or sulfur-containing heterocycle or an alkylgroup of 1 to 5 carbon atoms substituted therewith.

Examples of R⁹ groups include 1-methyl-3-pyrrolidinyl, furfuryl,2-thienylmethyl, 3-tetrahydrofuranyl, tetrahydrofurfuryl,tetrahydropyran-2-ylmethyl, 1,3-dioxolan-2-ylmethyl,2-(1,3-dioxolan-2-yl)ethyl, 2,2-dimethyl-1,3-dioxolan-4-ylmethyl,3-(2-methyl-1,3-dioxolan-2-yl)propyl, 1,3-dioxan-4-ylmethyl,1,4-benzodioxan-2-ylmethyl, tetrahydro-4H-pyran-4-yl,5,6-dihydro-2H-pyran-3-ylmethyl, 2,2-dimethyl-1,3-dithiolan-4-ylmethyl,tetrahydro-4H-thiopyran-4-yl, tetrahydrothien-3-yl,1-oxotetrahydrothien-3-yl, 1,1-dioxotetrahydrothien-3-yl,2,2-dimethyl-1,1,3,3-tetraoxo-1,3-dithiolan-4-ylmethyl,1,1-dioxotetrahydro-4H-thiopyran-4-yl, and 1,3-oxothiolan-2-ylmethyl.

For Z=--OSO₂ R¹⁰, R¹⁰ may be alkyl of 1 to 6(preferably 1 to 4) carbonatoms (which may be substituted with halogen, cyano, alkoxy or alkylthioof 1 to 4 carbon atoms, or alkylamino or dialkylamino in which alkyl isof 1 to 4 carbon atoms), phenyl, or alkylamino or dialkylamino in whichalkyl is of 1 to 4 carbon atoms. Examples of such Z substituents includephenylsulfonyloxy, methylsulfonyloxy, ethylsulfonyloxy,propylsulfonyloxy, butylsulfonyloxy, 1-methylethylsulfonyloxy,1-methylpropylsulfonyloxy, 2-methylpropylsulfonyloxy,3-methylbutylsulfonyloxy, chloromethylsulfonyloxy,3-chloropropylsulfonyloxy, trifluoromethylsulfonyloxy,methylaminosulfonyloxy, dimethylaminosulfonyloxy,dimethylaminoethylsulfonyloxy, 2-methoxyethylsulfonyloxy,2-ethoxyethylsulfonyloxy, and cyanomethylsulfonyloxy.

For Z=--NHN═C(R¹¹)(R¹²), one of R¹¹ and R¹² may be hydrogen or alkyl of1 to 4 carbon atoms and the other may be alkyl of 1 to 4 carbon atoms,or C(R¹¹)(R¹²) taken as a unit may be cycloalkyl of 3 to 7 (preferably 5to 7) carbon atoms. For example, Z may be NHN═C(CH₃)₂, NHN═CHCH₂ CH₃,NHN═C(CH₃)(C₂ H₅), ##STR4##

For ##STR5## n may be 0 to 2, preferably 0; R³ may be hydrogen or alkylof 1 to 4 carbon atoms; R⁴ may be hydrogen, alkyl of 1 to 4 carbonatoms, or alkoxy of 1 to 4 carbon atoms; Q and Q¹ may be independentlyO, S or NR⁷ in which R⁷ is hydrogen or alkyl of 1 to 6 (preferably 1 to4) carbon atoms; and R⁵ may be hydrogen, alkyl of 1 to 6 (preferably 1to 4) carbon atoms which may be substituted with cycloalkyl of 3 to 7carbon atoms (for example, methyl, cyclopropylmethyl, cyclopentylmethyl,or cyclohexylmethyl), cycloalkyl of 3 to 7 carbon atoms which may besubstituted with alkyl of 1 to 4 carbon atoms (for example,methylcyclopropyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, orcycloheptyl), alkoxyalkyl or alkylthioalkyl of 2 to 6 carbon atoms,haloalkyl of 1 to 5 carbon atoms (especially fluoroalkyl orchloroalkyl), alkenyl of 2 to 5 carbon atoms such as 2-propenyl,cycloalkenyl of 5 to 7 carbon atoms which may be substituted with alkylof 1 to 4 carbon atoms (for example, 2-cyclohexenyl), cycloalkenylalkylof 6 to 10 carbon atoms (for example, 3-cyclohexenylmethyl), phenyl orphenylmethyl (each of which may be ring-substituted with fluorine,chlorine, bromine, or alkyl, alkoxy, or alkylthio of 1 to 4 carbonatoms), cyanoalkyl of 1 to 5 alkyl carbon atoms such as cyanomethyl,alkynyl of 2 to 5 carbon atoms such as 2-propynyl, alkylimino of 1 to 6(preferably 1 to 4) carbon atoms which may be substituted withcycloalkyl of 3 to 7 carbon atoms, or cycloalkylimino of 5 to 7 carbonatoms which may be substituted with alkyl of 1 to 4 carbon atoms; or Q¹and R⁵ may together represent a phenylsulfonylamino group in which thephenyl is unsubstituted or substituted with halogen such as fluorine,chlorine, or bromine, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4carbon atoms, or alkoxycarbonyl of 1 to 4 alkyl carbon atoms.

This subgenus, especially where X¹ is 2-F and X² is Cl or Br, forms apreferred embodiment of the invention; particularly where n is 0 and oneof R³ and R⁴ is H and the other H, CH₃, C₂ H₅, OCH₃, or OC₂ H₅. Where Qor Q¹ is NR⁷, R⁷ is preferably H. Examaples of Z substituents where Q isNR⁷ include those of the formula --NHCH₂ CO₂ R⁵ and --NHCH(CH₃)CO₂ R⁵where R⁵ is methyl, ethyl, propyl, butyl, 2-methoxyethyl,2-propoxyethyl, 2-cyanoethyl, 2,3-dichloropropyl, 2,2-dichloroethyl,cyclopentylmethyl, cyclopentyl, 1-methylethyl, 1-ethylpropyl, or1-methylpropyl.

Thus, Z may be H or a substituent or group such as F, Cl, Br, I, NO₂,NH₂, CN, SO₃ H, alkyl haloalkyl, OR, SR, NR⁷ R, NHCO₂ -alkyl,N(CO-alkyl)₂, CO--R⁶, SO--R⁸ , SO₂ --R⁸, OR⁹, SR⁹, OSO₂ R¹⁰, NHN═CR¹¹R¹², O--CR³ R⁴ --CO₂ R⁵, O--CR³ R⁴ --CO--SR⁵, O--CR³ R⁴ --CO--NR⁷ R⁵,S--CR³ R⁴ --CO₂ R⁵, S--CR³ R⁴ --CO--SR⁵, S--CR³ R⁴ --CO--NR⁷ R⁵, NR⁷--CR³ R⁴ --CO₂ R⁵, NR⁷ --CR³ R⁴ --CO--SR⁵, or NR⁷ --CR³ R⁴ --CO--NR⁷ R⁵.

The aryl moiety of the present aryltriazinediones may be aheteroaromatic radical such as a furyl, thienyl, pyridyl, pyrimidyl,oxazolyl, pyrrolyl, isoxazolyl, thiazolyl, or isothiazolyl radical whichmay carry one or more substituents, for example, halogen and/or alkyl oralkoxy of 1 to 6 (preferably 1 to 4) carbon atoms. Preferably, however,the aryl moiety will be a phenyl radical, particularly a halophenylradical, more particularly a dihalophenyl radical.

In a preferred embodiment for herbicidal activity, the present compoundswill have the formula: ##STR6## in which X¹ and X² are both halogenatoms and Z is as defined above. X¹ is preferably chlorine or,especially, fluorine. X² is preferably chlorine or bromine.

With respect to the triazinedione portion of the molecule, R¹ may bealkyl of 1 to 6 (preferably 1 to 4) carbon atoms; haloalkyl of 1 to 5(preferably 1 to 3) carbon atoms; cyanoalkyl of 1 to 5 (preferably 1 to3) alkyl carbon atoms; alkenyl or alkynyl of 2 to 5 (preferably 3 to 5)carbon atoms; alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, oralkylsulfonylalkyl of 2 to 5 (preferably 2 to 4) carbon atoms; or amino.R¹ will frequently and conveniently be a lower alkyl group such asmethyl or ethyl, especially methyl. When R¹ is haloalkyl, the alkylradical may be substituted with one or more same or different halogenatoms, preferably the same and preferably fluorine. Typical fluoroalkylgroups include fluoromethyl, difluoromethyl, 2-fluoroethyl, and3-fluoropropyl. Examples of other R¹ substituents include cyanomethyl,amino, 2-propenyl, 2-propynyl, 2-methoxyethyl, methylthiomethyl,methylsulfinylmethyl, and methylsulfonylmethyl. In a preferredembodiment, R¹ is methyl or a fluoromethyl having 1 to 2 fluorine atoms,especially methyl.

R² may be hydrogen; halogen, especially fluorine, chlorine, or bromine;alkyl of 1 to 4 carbon atoms, especially methyl; haloalkyl of 1 to 4carbon atoms, particularly a fluoroalkyl such as trifluoromethyl;cyanoalkyl of 1 to 4 alkyl carbon atoms such as cyanomethyl; alkenyl of2 to 4 carbon atoms such as 2-propenyl; alkynyl of 2 to 4 carbon atomssuch as 2-propynyl; alkoxyalkyl of 2 to 4 carbon atoms, for example,2-methoxyethyl; amino; hydroxycarbonyl; or alkoxycarbonyl of 1 to 4alkyl carbon atoms. Compounds in which R² is hydroxycarbonyl, while inthemselves or as salts are generally herbicidal at high applicationrates, are more useful as intermediates (for the corresponding compoundsin which R² is hydrogen) than as herbicides. In a preferred embodiment,R² is hydrogen or methyl, especially hydrogen.

The groups W¹ and W² are independently selected from oxygen and sulfur.Thus, W¹ and W² may both be oxygen or sulfur, W¹ may be oxygen and W²may be sulfur, or W¹ may be sulfur and W² may be oxygen. In a preferredembodiment W¹ and W² are both oxygen.

A preferred subgenus for high herbicidal activity comprises thecompounds of the formula ##STR7## in which X² is bromine or chlorine andZ is as defined above. Compounds in which the fluorine atom at C-2 ofthe phenyl ring is replaced by a chlorine atom and Z is other thanhydrogen are also of particular interest.

It will be understood that any alkyl, alkenyl or alkynyl group hereinmay be straight chain or branched chain radicals. Thus, 1-methylethyl,2-methyl-2-propenyl, and 1-methyl-2-propynyl are branched chain examplesof alkyl, alkenyl, and alkynyl radicals respectively. Halogen may befluorine, chlorine, bromine, or iodine. Haloalkyl radicals may have oneor more same or different halogen atoms.

Any herbicidal compound of the present invention in which R² is CO₂ H orin which Z is or contains SO₃ H or CO₂ H may, of course, be convertedinto a salt such as a sodium, potassium, calcium, ammonium, magnesium,or mono-, di-, or tri(C₁ to C₄ alkyl)ammonium salt which may also beused as an herbicide. Such salts are within the scope of the presentinvention.

A number of the compounds of the invention may more readily exist inhydrated form rather than as non-hydrated materials. It will beunderstood that the presence or absence of water of hydrating in thecompounds is of no concern in determining the metes and bounds of thepresent invention.

The present compounds may be prepared by methods described in theliterature or by methods analogous or similar thereto and within theskill of the art.

Many of the present compounds may be prepared as illustrated in thefollowing chemical equations:

Method A: R² =H or CO₂ H ##STR8##

An appropriately substituted aniline, II, is treated first with aqueoushydrochloric acid, sodium acetate, and sodium nitrite, then withmalonyldiurethane and sodium acetate to produce intermediate III.Compound III is cyclized by treatment first with ethanolic potassiumhydroxide in tetrahydrofuran, then with aqueous hydrochloric acid togive the triazinedionecarboxylic acid Ic which is decarboxylated in thepresence of mercaptoacetic acid and xylene to give the intermediateCompound Id. Treatment of Id with R¹ Y, in which Y is a suitable leavinggroup, in the presence of a base gives the N-substituted triazinedioneIe.

Method B: R² =H, alkyl ##STR9##

An appropriately substituted aniline is reacted with sodium nitrite andtin (II) chloride in aqueous hydrochloric acid to produce thecorresponding hydrazine, Compound IV, which is converted to hydrazone Vby treatment with acetone in sulfuric acid and tetrahydrofuran.Treatment of V with potassium cyanate in aqueous acetic acid givestriazolidinone VI which upon reaction with R² COCO₂ H and sulfuric acidin dioxane produces triazinedione Ih. Reaction of Ih with R¹ Y wherein Yis a leaving group gives product Ii.

The methods illustrated above for producing Ie and Ii are generallyapplicable where the starting materials Compound II is readilyavailable, either commercially or by preparation, and the substituent Zis stable under the conditions of the process. In some instances thedesired Z substituent may be unstable under the conditions used inpreparing the starting material II or in converting II into product Ieor Ii. In such cases or where it is otherwise not desirable orconvenient to have the desired Z substituent in place at the outset, inCompound II, it may be advantageous to incorporate the desired Z groupinto the molecule further on in the process, for example, subsequent tothe addition of the R¹ group.

For example, the products in which Z is --OR⁹, --OSO₂ R¹⁰, --OCR³ R⁴CO--Q¹ R⁵, or --OR (R is other than lower alkyl) may advantageously beprepared from Compound Ie (or Ii) in which Z is lower alkoxy orbenzyloxy as illustrated in the following chemical equations: ##STR10##

In the equations above R¹³ represents the appropriate radical --R⁹,--SO₂ R¹⁰, --CR³ R⁴ --CO--Q¹ R⁵, or --R and Y represents a leavinggroup. The phenolic intermediate If is readily prepared from thecorresponding compound Ie in which Z is lower alkoxy or benzyloxy bytreatment with an acidic reagent such as concentrated sulfuric acid,concentrated hydrobromic acid, or a mixture of hydrobromic and aceticacids to effect dealkylation, or, where Z is benzyloxy, byhydrogenolysis over palladium on charcoal (H₂ /Pd/C/C₂ H₅ OH). Reactionof the 5-hydroxyphenyl intermediate If with the appropriate R⁹ --Y, R¹⁰--SO₂ Y, Y--CR³ R⁴ --CO--Q¹ R⁵, or R--Y, i.e., R¹³ --Y in the equationabove, in the presence of a base gives product Ig.

Similarly, products corresponding to Ie or Ii in which Z is --SR¹³,where R¹³ has the meaning given above, may be prepared by treatment ofthe corresponding 5-mercaptophenyl compound with R¹³ --Y. The5-mercaptophenyl compound may be prepared from the correspondingcompound in which Z is hydrogen (Ie or Ii, Z=H) by the sequence of stepsillustrated below: ##STR11## Compound Ie in which Z is hydrogen may benitrated to give the corresponding 5-nitro compound Ij, which may bereduced to give the corresponding 5-amino compound Ik. Compound Ik maybe treated first with NaNO₂ /HCl, then with SO₂ /CuCl to give the5-chlorosulfonyl compound Il which may be reduced with Sn/HCl to givethe corresponding 5-mercapto compound Im.

As with the 5-OH and 5-SH intermediates, the 5-NH₂ compound, Ik, is animportant intermediate which may be alkylated or acylated to introduceother Z substituents into the molecule. Compounds in which Z isalkoxycarbonylamino, di(alkylcarbonyl)amino, --NR⁷ R, or --NR⁷ --CR³ R⁴--CO--Q¹ R⁵ may be prepared in this manner from the corresponding 5-NH₂compound. An alternative method for introducing certain --NHR or--NH--CR³ R⁴ --CO--Q¹ R⁵ Z groups is illustrated in the equation below:##STR12## For example, Compounds 89 (Z=--NHCH(CH₃)₂), 206(Z=--NH-cyclohexyl), and 232 (Z=--NH--CH(CH₃)--CO₂ C₂ H₅) shown in Table1 below were prepared by condensing the corresponding 5-NH₂ compoundwith the appropriate ketone in the presence of borane intetrahydrofuran.

The compound of formula Ie or Ii in which Z is --NHN═CR¹¹ R¹² may alsobe produced from the corresponding compound in which Z is --NH₂ byreacting the 5-NH₂ compound with NaNO₂ and SnCl₂ in aqueous HCl to givethe corresponding hydrazine (Ie, Z=--NHNH₂), followed by condensationwith R¹¹ COR¹².

The amino compounds (Ie or Ii, Z=--NH₂) may also be converted into thecorresponding compounds in which Z is a halogen atom by treatment withnitrous acid under conditions which give a diazonium salt followed bytreatment of the salt with the appropriate halogen reagent, for example,CuCl, CuBr, KI, or HBF₄.

The compounds of formula I in which W¹ or W² or both are sulfur may beprepared as follows. Compound Ie or Ii may be treated with oneequivalent of P₂ S₅ in pyridine to give the corresponding compound offormula I in which W² is sulfur; or Ie or Ii may be treated with atleast two equivalents of P₂ S₅ to produce the dithione derivative (I, W¹=W² =S). Compound I in which W¹ is sulfur and W² is oxygen may beprepared by substituting KSCN for KOCN in Method B above to produce thetriazolidinethione corresponding to the triazolidinone VI which may thenbe carried through the Method B process to give the1,2,4-triazine-3-thione-5-one product.

The novel intermediates for the present herbicidal compounds are alsopart of the present invention, particularly compounds VII, VIII, IX, andX. ##STR13##

In each of the compounds above, X¹, X², W¹, and W² are as defined above.Preferably X¹ and X² are both halogen, especially fluorine, chlorine, orbromine. In a particularly preferred embodiment, X¹ is chlorine or,especially, fluorine and X² is chlorine or bromine. W¹ and W² arepreferably both oxygen.

For compound VII, R¹⁵ is an alkyl group, preferably of 1 to 4 carbonatoms, which may be substituted or unsubstituted, and:

Z is fluorine, chlorine, bromine, iodine, cyano, nitro, amino,alkoxycarbonylamino of 1 to 6 alkyl carbon atoms, di(alkylcarbonyl)aminoin which each alkyl is of 1 to 6 carbon atoms, hydroxysulfonyl,halosulfonyl, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 5 carbonatoms, --QR, --CO--R⁶, --S(O)_(m) R⁸, --Q² R⁹, --OSO₂ R¹⁰, NHN═CR¹¹ R¹²,or --Q--CR³ R⁴ --CO--Q¹ --R⁵ ;

Q and Q¹ are independently O, S, or NR⁷ in which R⁷ is hydrogen or alkylof 1 to 6 carbon atoms;

Q² is O or S;

R is hydrogen, alkyl of 1 to 6 carbon atoms (which is unsubstituted orsubstituted with cycloalkyl of 3 to 7 carbon atoms), cycloalkyl of 3 to7 carbon atoms (which is unsubstituted or substituted with alkyl of 1 to6 carbon atoms), benzyl, alkoxyalkyl of 2 to 8 carbon atoms,alkoxyalkoxyalkyl of 3 to 8 carbon atoms, alkylthioalkyl,alkylsulfinylalkyl, or alkylsulfonylalkyl of 2 to 8 carbon atoms,tri(alkyl of 1 to 4 carbon atoms)silyl(alkyl of 1 to 4 carbon atoms),cyanoalkyl of 1 to 5 alkyl carbon atoms, alkenyl or haloalkenyl of 2 to5 carbon atoms, alkynyl or haloalkynyl of 2 to 5 carbon atoms, haloalkylof 1 to 5 carbon atoms, alkylcarbonyl of 1 to 6 alkyl carbon atoms, ordialkylaminocarbonyl or dialkylaminothiocarbonyl in which each alkyl isof 1 to 6 carbon atoms;

R³ is hydrogen or alkyl of 1 to 4 carbon atoms, and R⁴ is hydrogen,alkyl of 1 to 4 carbon atoms, or alkoxy of 1 to 4 carbon atoms;

R⁵ is hydrogen, alkyl of 1 to 6 carbon atoms (which is unsubstituted orsubstituted with cycloalkyl of 3 to 7 carbon atoms), cycloalkyl of 3 to7 carbon atoms (which is unsubstituted or substituted with alkyl of 1 to4 carbon atoms), alkoxyalkyl or alkylthioalkyl of 2 to 6 carbon atoms,haloalkyl or 1 to 5 carbon atoms, alkenyl of 2 to 5 carbon atoms,cycloalkenyl of 5 to 7 carbon atoms (which is unsubstituted orsubstituted with alkyl of 1 to 4 carbon atoms), cycloalkenylalkyl of 6to 10 carbon atoms, phenyl or phenylmethyl (each of which isunsubstituted or ring-substituted with fluorine, chlorine, bromine, oralkyl, alkoxy or alkylthio of 1 to 4 carbon atoms), cyanoalkyl of 1 to 5alkyl carbon atoms, alkynyl of 2 to 5 carbon atoms, alkylimino of 1 to 6carbon atoms (which is unsubstituted or substituted with cycloalkyl of 3to 7 carbon atoms), or cycloalkylimino of 5 to 7 carbon atoms (which isunsubstituted or substituted with alkyl of 1 to 4 carbon atoms); or Q¹and R⁵ together represent a phenylsulfonylamino group in which thephenyl is unsubstituted or substituted with fluorine, chlorine, bromine,alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, oralkoxycarbonyl of 1 to 4 alkyl carbon atoms;

R⁶ is hydroxy, alkoxy or alkylthio of 1 to 6 carbon atoms, alkoxyalkoxyof 2 to 6 carbon atoms, amino, or alkylamino or dialkylamino whereineach alkyl is of 1 to 6 carbon atoms and is unsubstituted or substitutedwith alkoxy of 1 to 4 carbon atoms;

R⁸ is alkyl of 1 to 6 carbon atoms or alkenyl or alkynyl of 2 to 5carbon atoms and m is 1 or 2;

R⁹ is a 5- or 6-membered ring heterocyclic group of 1 or 2 same ordifferent heteroatoms selected from O, S, and N or an alkyl radical of 1to 5 carbon atoms substituted with said heterocyclic group;

R¹⁰ is alkyl of 1 to 6 carbon atoms (which is unsubstituted orsubstituted with halogen, cyano, alkoxy or alkylthio of 1 to 4 carbonatoms, or alkylamino or dialkylamino in which alkyl is of 1 to 4 carbonatoms), phenyl, or alkylamino or dialkylamino in which alkyl is of 1 to4 carbon atoms; and

R¹¹ is hydrogen or alkyl of 1 to 4 carbon atoms and R¹² is alkyl of 1 to4 carbon atoms, or C(R¹¹)(R¹²) taken as a unit is cycloalkyl of 3 to 7carbon atoms.

Preferably Z is fluorine, chlorine, bromine, iodine, cyano, nitro,amino, hydroxysulfonyl, chlorosulfonyl, or a group --OR in which R isalkyl of 1 to 6 carbon atoms, benzyl, alkoxyalkyl of 2 to 4 carbonatoms, or alkenyl or alkynyl of 2 to 5 carbon atoms. In a particularlypreferred embodiment Z is --OR in which R is alkyl of 1 to 4 carbonatoms or benzyl.

For compound VIII (R¹ =H), Z is as defined above for compound VII and R²is hydrogen, hydroxycarbonyl, or alkyl of 1 to 4 carbon atoms such asmethyl. R² is preferably hydrogen or hydroxycarbonyl.

For compound IX (R² =CO₂ H), Z is as defined above for compound VII andR^(I) is alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 5 carbon atoms,cyanoalkyl of 1 to 5 alkyl carbon atoms, alkenyl or alkynyl of 2 to 5carbon atoms, alkoxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, oralkylsulfonylalkyl of 2 to 5 carbon atoms. R¹ is preferably alkyl of 1to 4 carbon atoms, cyanoalkyl of 1 to 3 alkyl carbon atoms, fluoroalkylof 1 to 3 carbon atoms, alkenyl or alkynyl of 3 to 5 carbon atoms,alkoxyalkyl of 2 to 4 carbon atoms, alkylthioalkyl of 2 to 4 carbonatoms, alkylsulfinylalkyl of 2 to 4 carbon atoms, or alkylsulfonylalkylof 2 to 4 carbon atoms. For example, R¹ may be methyl, ethyl,cyanomethyl, 2-propenyl, 2-propynyl, fluoromethyl having 1 or 2 fluorineatoms, 2-fluoroethyl, 3-fluoropropyl, methoxymethyl, methylthiomethyl,methylsulfinylmethyl, or methylsulfonylmethyl, especially methyl.

For compound X (Z=OH, SH, or NH₂), R¹ is as defined above for compoundIX and R² is hydrogen or alkyl of 1 to 4 carbon atoms such as methyl, R²is preferably hydrogen.

Representative compounds of the invention are shown in Table 1.Characterizing data for many of the compounds are given in Table 2.

The preparation and herbicidal activity of representative compounds ofthis invention are illustrated further in the examples below. Alltemperatures are in degrees Celsius, and all pressures are in mm Hg.

EXAMPLE I2-(2,4-DICHLOROPHENYL)-4,6-DIMETHYL-1,2,4-TRIAZINE-3,5-(2H,4H)-DIONEStep A 2-(2,4-Dichlorophenyl)-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione

To a stirred solution of 4.32 g (0.020 mole) of2,4-dichlorophenylhydrazine hydrochloride in 100 mL of water and 50 mLof ethanol was added dropwise 2.14 g (0.024 mole) of pyruvic acid in 50mL of water. Upon complete addition, a precipitate formed and wascollected by filtration and dried under reduced pressure at ambienttemperature. The solid hydrazone product was dissolved in 100 mL oftoluene to which 4.8 g (0.041 mole) of thionyl chloride was added. Theresultant mixture was stirred and heated at reflux for 0.5 hour.Distillation of the solvent under reduced pressure left a solid residue,which was dissolved in 100 mL of toluene. Urethane (2.2 g, 0.024 mole)was added, and the resultant solution heated at reflux with stirring fortwo hours. The solvent was removed from the mixture by distillationunder reduced pressure to leave a residue. This residue was subjected tocolumn chromatography on silica gel, eluting with ethyl acetate:heptane(1:1). Appropriate fractions were combined, and the solvent removed byevaporation to leave a gummy residue. The residue was dissolved in 75 mLof ethanol and 75 mL of 1N sodium hydroxide. The resultant solution washeated to 60° C., then poured into a mixture of 3N hydrochloric acid andice. A solid formed which was collected by filtration and dried underreduced pressure. Recrystallization from tetrahydrofuran:heptaneprovided 2.0 g of2-(2,4-dichlorophenyl)-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione (mp 197°C. dec), Compound 4 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

Step B2-(2,4-Dichlorophenyl)-4,6-dimethyl-1,2,4-triazine-3,5(2H,4H)-dione

A solution of 1.1 g (0.0040 mole) of2-(2,4-dichlorophenyl)-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione in 5 mLof N,N-dimethylformamide was added to a stirred mixture of 0.11 g(0.0045 mole) of sodium hydride in 10 mL of N,N-dimethylformamide. After0.5 hour, 0.63 g (0.0045 mole) of iodomethane in 5 mL ofN,N-dimethylformamide was added, and the resultant mixture was stirredfor approximately 18 hours. The mixture was poured into water and theresulting precipitate was collected and dissolved in ethyl acetate. Theorganic solution was washed with water, dried over anhydrous magnesiumsulfate, and filtered. The filtrate was evaporated under reducedpressure to leave a solid. The solid was purified by recrystallizationfrom heptane to yield 0.52 g of2-(2,4-dichlorophenyl)-4,6-dimethyl-1,2,4-triazine-3,5(2H,4H)-dione (mp109°-110° C.), Compound 5 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

EXAMPLE II2-[4-CHLORO-2-FLUORO-5-(1-METHYLETHOXY)PHENYL]-1,2,4-TRIAZINE-3,5(2H,4H)-DIONEStep A Methyl(2-chloro-4-fluorophenyl)carbonate

To a stirred solution of 20.0 g (0.14 mole) of 2-chloro-4-fluorophenoland 6.64 g (0.17 mole) of sodium hydroxide in 100 mL of water at 15° C.was added 17.7 g (0.19 mole) of methyl chloroformate. After completeaddition, the mixture was stirred for 15 minutes then extracted withethyl acetate. The organic phase was washed with a 1N sodium hydroxidesolution, then dried over anhydrous magnesium sulfate. The dried extractwas filtered, and the filtrate evaporated under reduced pressure toprovide methyl(2-chloro-4-fluorophenyl)carbonate as a solid.

Step B 2-Chloro-4-fluoro-5-nitrophenol

To a stirred mixture of methyl(2-chloro-4-fluorophenol)carbonateprepared in Step A in 21.7 mL of concentrated sulfuric acid was addeddropwise 11.1 mL of concentrated nitric acid. The reaction mixture waskept at a temperature below 30° C. throughout the addition. Aftercomplete addition, the mixture was stirred at room temperature for onehour, then poured into 500 mL of ice water. The aqueous mixture wasextracted with ethyl acetate. The extract was washed in succession withwater, saturated aqueous sodium bicarbonate, and saturated aqueoussodium chloride. The washed extract was dried over anhydrous magnesiumsulfate, filtered, and the filtrate was evaporated under reducedpressure to leave a solid residue,methyl(2-chloro-4-fluoro-5-nitrophenyl)carbonate. This residue wasdissolved in 100 mL of ethanol to which was added 150 mL of a 1N sodiumhydroxide solution. The mixture was heated on a steam bath for 30minutes, cooled, and poured into a mixture of ice and hydrochloric acid.The resultant acidic mixture was extracted with ethyl acetate. Theextract was dried over anhydrous magnesium sulfate and was filtered. Thefiltrate was evaporated under reduced pressure to give an oil whichcrystallized slowly. Recrystallization from heptane gave 15.8 g of2-chloro-4-fluoro-5-nitrophenol.

The nmr spectrum was consistent with the assigned structure.

Step C 4-Chloro-2-fluoro-5-(1-methylethoxy)nitrobenzene

To a stirred solution of 15.8 g (0.083 mole) of2-chloro-4-fluoro-5-nitrophenol in 90 mL of acetone was added 17.1 g(0.12 mole) of potassium carbonate followed by a solution of 21.0 g(0.12 mole) of 2-iodopropane in 10 mL of acetone. After completeaddition, the reaction mixture was heated at 60° C. for approximately 18hours. The mixture was cooled and poured into a mixture of ice andconcentrated hydrochloric acid. The resultant mixture was extracted withethyl acetate, and the extract was washed with a 1N sodium hydroxidesolution. The washed extract was dried over anhydrous magnesium sulfateand was filtered. The solvent was evaporated under reduced pressure toleave 17.7 g of 4-chloro-2-fluoro-5-(1-methylethoxy)nitrobenzene as asolid.

Step D2-[4-Chloro-2-fluoro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5(2H,4H)-dione

Hydrogenation of 2.8 g (0.012 mole) of4-chloro-2-fluoro-5-(1-methylethoxy)nitrobenzene in the presence of 30mL of acetic acid and 0.2 g of platinum oxide produced4-chloro-2-fluoro-5-(1-methylethoxy)aniline, which was not isolated fromthe reaction mixture. The platinum catalyst was removed by filtration,and the filtrate was diluted with 100 mL of water and 10 mL ofconcentrated hydrochloric acid. The acid solution was cooled to 0° C.,and a solution of 0.84 g (0.012 mole) of sodium nitrite in 10 mL ofwater was added. The solution was stirred at 0° C. for 30 minutes, thena solution of 5.0 g (0.061 mole) of sodium acetate in 10 mL of water wasadded. After stirring for a short period of time, the solution was addedto a mixture of 3.0 g (0.12 mole) of malonyldiurethane [prepared by themethod of Backes, et al., J. Chem. Soc., 359, (1921)] and 25.0 g (0.29mole) of anhydrous sodium acetate in 300 mL of water at 10° C. Aftercomplete addition, the mixture was stirred at 10° C. for 30 minutes. Themixture was extracted with ethyl acetate, and the extract washed with asaturated aqueous sodium chloride solution. The washed extract was driedover anhydrous magnesium sulfate, filtered, and the filtrate evaporatedunder reduced pressure to give 6.0 g of a solid.

The solid was dissolved in a mixture of 80 mL of ethanol and 80 mL oftetrahydrofuran. To this was added 40 mL of a 10% aqueous potassiumhydroxide solution. The resultant mixture was stirred for 15 minutes andwashed with ethyl acetate. The aqueous phase was made acidic with dilutehydrochloric acid, and the acidic solution extracted with ethyl acetate.The extract was treated with decolorizing charcoal and dried overanhydrous magnesium sulfate. The extract was filtered, and the filtratewas concentrated under reduced pressure to leave 3.2 g of a residue. Theresidue was heated at 150° C. in 6.0 mL of mercaptoacetic acid for threehours. The mixture was cooled to room temperature, diluted with ethylacetate, and extracted with a saturated aqueous sodium bicarbonatesolution. The organic phase was dried over anhydrous magnesium sulfateand filtered. The solvent was evaporated from the filtrate under reducedpressure to yield 2.0 g of2-[4-chloro-2-fluoro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5(2H,4H)-dioneas an oil, Compound 17 in the tables.

The nmr spectrum was consistent with the assigned structure.

EXAMPLE III2-[2,4-DICHLORO-5-(2-PROPYNYLOXY)PHENYL]-4-METHYL-1,2,4-TRIAZINE-3,5(2H,4H)-DIONEStep A 3-Hydroxyacetanilide

To a stirred solution of 66.0 g (0.60 mole) of 3-aminophenol in 180 mLof water was added dropwise 77.9 g (0.76 mole) of acetic anhydride.After complete addition, the reaction mixture was heated on a steam bathfor 10 minutes, then cooled to 0° C. A precipitate formed and wascollected by filtration. The filter cake was washed with cold water anddried in a desiccator for two hours to yield 81.0 g of3-hydroxyacetanilide (mp 144°-146° C.).

Step B 2,4-Dichloro-5-hydroxyacetanilide

Chlorination of 53.0 g (0.35 mole) of 3-hydroxyacetanilide with chlorinegas in 400 mL of glacial acetic acid at 15°-20° C. for one hour produced23.5 g of 2,4-dichloro-5-hydroxyacetanilide (mp 226°-228° C.).

Step C 2,4-Dichloro-5-(1-methylethoxy)acetanilide

A stirred mixture of 22.0 g (0.1 mole) of2,4-dichloro-5-hydroxyacetanilide, 25.5 g (0.15 mole) of 2-iodopropane,and 20.7 g (0.15 mole) of potassium carbonate in 150 mL of acetone washeated at reflux temperature for approximately 18 hours. The mixture wascooled, filtered, and the filtrate evaporated under reduced pressure toleave a solid. The solid was recrystallized from ethanol to yield 22.3 gof 2,4-dichloro-5-(1-methylethoxy)acetanilide (mp 129°-130° C.).

Step D 2,4-Dichloro-5-(1-methylethoxy)aniline

A stirred mixture of 22.3 g of 2,4-dichloro-5-(1-methylethoxy)acetanilide, 60 mL of concentrated hydrochloric acid, and 60 mL of waterwas heated at reflux for 0.5 hour. The mixture was cooled in arefrigerator, and the resulting precipitate was collected by filtration.The solid was suspended in water, and the mixture was treated withsodium carbonate until it was slightly basic. The resultant mixture wasextracted with diethyl ether. The extract was washed with water, and theether removed by distillation under reduced pressure to leave an oil.Distillation of the oil under reduced pressure produced 14.0 g of2,4-dichloro-5-(1-methylethoxy)aniline (bp 102° C. at 0.1 mm Hg).

Step E2-[2,4-Dichloro-5-(1-methylethoxy)-phenyl]-1,2,4-triazine-3,5(2H,4H)-dione-6-carboxylicacid

To a stirred mixture of 10.0 g (0.045 mole) of2,4-dichloro-5-(1-methylethoxy)aniline in 200 mL of water was added 30mL of concentrated hydrochloric acid. The resultant mixture was cooledto 0° C., and a solution of 3.13 g (0.45 mole) of sodium nitrite in 30mL of water was added during 15 minutes. After complete addition, 30.0 g(0.35 mole) sodium acetate in 60 mL of water was added, and theresulting mixture was stirred at 0° C. for one hour. The cold reactionmixture was added portionwise to a stirred solution of 11.7 g (0.0477mole) of malonyldiurethane [prepared by the method of Backes, et al., J.Chem. Soc., 350, (1921)] and 50.0 g (0.59 mole) of anhydrous sodiumacetate in 1500 mL of water at 0° C. After complete addition the mixturewas stirred at 0° C. for one hour, and the resulting precipitate wascollected by filtration and washed with water. The filter cake wasdissolved in a mixture of 250 mL of tetrahydrofuran and 250 mL ofethanol. To this solution was added 150 mL of a 10% aqueous potassiumhydroxide solution. The resultant mixture was stirred for 0.5 hour andmade acidic with 60 mL of concentrated hydrochloric acid. Most of thetetrahydrofuran was removed from the mixture by evaporation underreduced pressure to leave an aqueous residue. The residue was extractedwith ethyl acetate, and the extract treated with decolorizing charcoal.The extract was dried over anhydrous magnesium sulfate and filtered. Thefiltrate was evaporated under reduced pressure to leave 17.9 g of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5(2H,4H)-dione-6-carboxylicacid, Compound 11 in the tables.

The preparation of Compound 11 was repeated. The product was found tohave a melting point of 195°-197° C. (dec.) and its nmr and ir spectrawere consistent with the assigned structure.

Step F2-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5(2H,4H)-dione

A stirred mixture of 10.0 g (0.028 mole) of2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5-(2H,4H)-dione-6-carboxylicacid in 10 mL of mercaptoacetic acid was heated at 140° C. for twohours. The reaction mixture was cooled to room temperature andpartitioned between ethyl acetate and saturated aqueous sodiumbicarbonate. The organic phase was washed with two portions of saturatedaqueous sodium bicarbonate, and then with saturated aqueous sodiumchloride. The washed organic phase was dried over anhydrous magnesiumsulfate and filtered. The filtrate was evaporated under reduced pressureto yield 7.5 g of2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5(2H,4H)-dione,Compound 51 in the tables.

Compound 6 in the tables was prepared in a similar manner (Step E and F)from the appropriately substituted aniline.

Step G2-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-4-methyl-1,2,4-triazine-3,5(2H,4H)-dione

To a stirred mixture of 0.6 g (0.025 mole) of sodium hydride in 15 mL ofN,N-dimethylformamide was added a solution of 7.5 g (0.024 mole) of2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5(2H,4H)-dionein 30 mL of N,N-dimethylformamide with external cooling to maintain thereaction temperature below 40° C. After complete addition, the mixturewas allowed to come to room temperature and was stirred for one hour. Asolution of 3.5 g (0.025 mole) of iodomethane in 10 mL ofN,N-dimethylformamide was added to the reaction mixture, and stirringwas continued for an additional hour at room temperature. The reactionmixture was poured into ice water, and the mixture was extracted withethyl acetate. The extract was dried over anhydrous magnesium sulfateand filtered. The filtrate was evaporated under reduced pressure toproduce2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4-methyl-1,2,4-triazine-3,5(2H,4H)-dioneas an oil, Compound 12 in the tables.

The preparation of Compound 12 was repeated. The product was found tohave a melting point of 111°-112° C. after chromatographic purificationon a silica gel column. The nmr and ir spectra of this sample wereconsistent with the assigned structure. Compounds 2, 7, 8, and 18 werealso prepared in this manner from the appropriately substituted anilines(prepared by the methods of Example III, Steps E and F) and iodomethane.Compounds 3, 15 and 19 were prepared from 3-bromo-1-propene and theappropriately substituted triazinedione. Similarly, reaction of theappropriately substituted triazinedione with propargyl bromide,bromoethane, and 1-chloro-2-fluoroethane gave Compounds 25, 29, and 41respectively.

Step H2-(2,4-Dichloro-5-hydroxyphenyl)-4-methyl-1,2,4-triazine-3,5(2H,4H)-dione

The oil prepared in Step G (Compound 12) was stirred with 10 mL ofconcentrated sulfuric acid at 0° C. for 10 minutes, and the mixture waspoured into ice water. The aqueous mixture was extracted with ethylacetate, and the solvent was removed from the extract by evaporationunder reduced pressure to give a residue. The residue was purified bycolumn chromatography on silica gel, eluting with ethyl acetate:heptane(1:1). Evaporation of the appropriate fractions gave 4.4 g of2-(2,4-dichloro-5-hydroxyphenyl)-4-methyl-1,2,4-triazine-3,5-(2H,4H)-dione(mp 199°-201° C.), Compound 9 in the tables.

The nmr spectrum was consistent with the assigned structure.

Step I2-[2,4-Dichloro-5-(2-propynyloxy)phenyl]-4-methyl-1,2,4-triazine-3,5(2H,4H)-dione

Under a dry nitrogen atmosphere a solution of 1.0 g (0.003 mole) of2-(2,4-dichloro-5-hydroxyphenyl)-4-methyl-1,2,4-triazine-3,5(2H,4H)-dionein 15 mL of N,N-dimethylformamide was added slowly to a stirred mixtureof 0.09 g (0.0037 mole) of sodium hydride in 15 mL ofN,N-dimethylformamide. After complete addition, the mixture was stirredat 28° C. until hydrogen evolution ceased, then at 45° C. for 30minutes. The reaction mixture was cooled to room temperature, and asolution of 0.57 g (0.0038 mole) of 3-bromo-1-propyne in 5 mL ofN,N-dimethylformamide was added. The mixture was stirred at roomtemperature for approximately 18 hours, poured into water, and extractedwith ethyl acetate. The extract was washed with a saturated aqueoussodium chloride solution, dried over anhydrous magnesium sulfate, andfiltered. The solvent was removed from the filtrate by evaporation underreduced pressure to leave an oil. The oil was purified by preparativechromatography on silica gel, eluting with ethyl acetate:heptane (1:1),to yield 0.8 g of2-[2,4-dichloro-5-(2-propynyloxy)phenyl]-4-methyl-1,2,4-triazine-3,5(2H,4H)-dione(mp 119°-120° C.), Compound 20 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

Compound 21,2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4-methyl-1,2,4-triazine-3,5(2H,4H)-dione,was also prepared by the method of Example III, Steps H and I, from theappropriately substituted triazinedione.

EXAMPLE IV2-[2,4-DICHLORO-5-(1-METHYLETHOXY)PHENYL]-4,6-DIMETHYL-1,2,4-TRIAZINE-3,5(2H,4H)-DIONEStep A 2,4-Dichloro-5-(1-methylethoxy)phenylhydrazine

A solution of 15.8 g (0.23 mole) of sodium nitrite in 100 mL of waterwas added to a stirred solution of 50.0 g (0.23 mole) of2,4-dichloro-5-(1-methylethoxy)aniline in 250 mL of concentratedhydrochloric acid at 0° C. over 30 minutes. After complete addition, themixture was stirred at 0° C. for 30 minutes. A solution of 114.0 g(0.506 mole) of tin (II) chloride dihydrate in 125 mL of concentratedhydrochloric acid was added dropwise to the reaction mixture. Aftercomplete addition, the mixture was stirred for one hour. The resultantwhite slurry was filtered. The filter cake was added to a 20% aqueoussodium hydroxide solution and stirred for 30 minutes. The basic mixturewas filtered, and the filter cake recrystallized from methanol and waterto yield 37.0 g of 2,4-dichloro-5-(1-methylethoxy)phenylhydrazine.

Step B1-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-3,3-dimethyl-1,2,4-triazolidin-5-one

To a stirred solution of 12.7 g (0.054 mole) of2,4-dichloro-5-(1-methylethoxy)phenylhydrazine in a mixture of 100 mL oftetrahydrofuran and 30 mL of acetone was added 0.5 mL of a 2N sulfuricacid solution. The reaction mixture was stirred at room temperature for30 minutes after which the solvent was removed by evaporation underreduced pressure. The residue was dissolved in ethyl acetate, and theorganic solution was washed with water. The washed organic solution wasdried over anhydrous magnesium sulfate, filtered, and the filtrateevaporated under reduced pressure leaving 14.6 g of an oil. The oil wasdissolved in 50 mL of glacial acetic acid and 2 mL of water. To thissolution was added portionwise 4.5 g (0.56 mole) of potassium cyanate.After complete addition, the mixture was stirred at room temperature forapproximately 18 hours. An additional 0.5 g of potassium cyanate wasadded, and the reaction mixture was stirred for five hours. The mixturewas then diluted with water and extracted with ethyl acetate. Theextract was dried over anhydrous magnesium sulfate, filtered, and thefiltrate evaporated under reduced pressure leaving an oil. The oil wasdissolved in 20 mL of ethyl acetate and, upon the addition of 10 mL ofheptane, formed a precipitate. The precipitate was collected byfiltration and recrystallized from ethyl acetate and heptane to give 4.5g of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3,3-dimethyl-1,2,4-triazolidin-5-one(mp 162°-163° C.).

The nmr and ir spectra were consistent with the assigned structure.

Step C2-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-6-methyl-1,2,4-triazine-3,5(2H,4H)-dione

To a stirred mixture of 1.0 g (0.0031 mole) of1-[2,4-dichloro-5-(1-methylethoxy)phenyl]-3,3-dimethyl-1,2,4-triazolidin-5-onein 10 mL of p-dioxane was added 0.29 g (0.0031 mole) of pyruvic acid andone drop of concentrated sulfuric acid. The mixture was stirred at roomtemperature for one hour, then an additional 0.25 g (0.0029 mole) ofpyruvic acid was added. The mixture was heated at 90° C. for threehours, then poured into water. The mixture was extracted with ethylacetate, and the solvent was evaporated from the extract under reducedpressure to give an oil. The oil was purified by thin-layer preparativechromatography on silica gel, eluting with ethyl acetate:heptane (1:1).Extraction of the appropriate bands gave 0.6 g of2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-6-methyl-1,2,4-triazine-3,5(2H,4H)-dioneas a solid (mp 163°-164° C.), Compound 10 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

Step D2-[2,4-Dichloro-5-(1-methylethoxy)phenyl]-4,6-dimethyl-1,2,4-triazine-3,5(2H,4H)-dione

In a manner similar to Example III, Step G, the reaction of 0.28 g(0.00085 mole) of2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-6-methyl-1,2,4-triazine-3,5(2H,4H)-dionewith 0.037 g (0.00093 mole) of sodium hydride (60% in oil) and 0.13 g(0.00093 mole) of iodomethane in 10 mL of N,N-dimethylformamide produced0.19 g of2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4,6-dimethyl-1,2,4-traizine-3,5(2H,4H)-dioneas a low melting solid, Compound 13 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

Compound 16,2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-6-methyl-4-(2-propenyl)-1,2,4-triazine-3,5(2H,4H)-dione,was also prepared by the method of Example IV using 3-bromo-1-propenerather than iodomethane in Step D. Similarly, Compound 50,2-[4-chloro-2-fluoro-5-(1-methylethoxy)phenyl]-4-(3-fluoropropyl)-1,2,4-triazine-3,5(2H,4H)-dione,was prepared by treating Compound 17 (Example II D) with1-chloro-3-fluoropropane.

EXAMPLE V2-[2,4-DICHLORO-5-(1-METHYLETHOXY)PHENYL]-4-METHYL-1,2,4-TRIAZINE-3,5(2H,4H)-DIONE-6-CARBOXYLICACID

In a manner similar to Example III, Step G, the reaction of 6.6 g (0.018mole) of2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5(2H,4H)-dione-6-carboxylicacid (Compound 11, Example III E) with 1.5 g (0.037 mole) of sodiumhydride (60% in oil) and 2.6 g (0.018 mole) of iodomethane in 35 mL ofN,N-dimethylformamide produced 2.1 g of2-[2,4-dichloro-5-(1-methyethoxy)phenyl]-4-methyl-1,2,4-triazine-3,5-(2H,4H)-dione-6-carboxylicacid as a solid (mp 230° C. d), Compound 14 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

EXAMPLE VI ETHYL2,4-DICHLORO-5-[4-METHYL-1,2,4-TRIAZINE-3,5(2H,4H)-DIONE-2-YL]-PHENOXYACETATE

In a manner similar to Example II, Step C, the reaction of 0.86 g(0.0030 mole) of2-(2,4-dichloro-5-hydroxyphenyl)-4-methyl-1,2,4-triazine-3,5(2H,4H)-dione(Compound 9, Example III H) with 0.62 g (0.0045 mole) of potassiumcarbonate and 0.75 g (0.0045 mole) of ethyl bromoacetate in 10 mL ofacetone produced an oil. The oil crystallized upon treatment withheptane to yield 0.85 g of ethyl2,4-dichloro-5-[4-methyl-1,2,4-triazine-3,5(2H,4H)-dione-2-yl]phenoxyacetate(mp 115°-117° C.), Compound 22 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

Compounds 27 and 28 were prepared in a similar manner by treatment ofCompound 9 with ethyl 2-bromopropionate and chloroacetonitrilerespectively. The nmr and ir spectra were consistent with the assignedstructures.

EXAMPLE VII2-(2,4-DICHLORO-5-METHYLSULFONYLOXYPHENYL)-4-METHYL-1,2,4-TRIAZINE-3,5(2H,4H)-DIONE

A solution of 0.35 g (0.0031 mole) of methanesulfonyl chloride in 5 mLof tetrahydrofuran was added to a stirred solution of 0.8 g (0.0028mole) of2-(2,4-dichloro-5-hydroxyphenyl)-4-methyl-1,2,4-triazine-3,5-(2H,4H)-dione(Compound 9, Example III H) and 0.30 g (0.0031 mole) of triethylamine in10 mL of tetrahydrofuran. The reaction mixture was stirred at roomtemperature for approximately 18 hours, then diluted with water. Theresultant mixture was extracted with ethyl acetate, and the extract wasdried over anhydrous magnesium sulfate. The dried extract was filtered,and the filtrate was evaporated under reduced pressure to give 0.81 g of2-(2,4-dichloro-5-methylsulfonyloxyphenyl)-4-methyl-1,2,4-triazine-3,5(2H,4H)-dioneas a solid, Compound 23 in the tables.

The nmr and ir spectra were consistent with the assigned structure.

EXAMPLE VIII2-[2,4-DICHLORO-5-(1-METHYLETHOXY)PHENYL]-4-(2-FLUOROETHYL)-1,2,4-TRIAZINE-3,5(2H,4H)-DIONE

To a stirred mixture of 0.084 g (0.0035 mole) of sodium hydride in 20 mLof tetrahydrofuran was added a solution of 1.0 g (0.003 mole) of2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-1,2,4-triazine-3,5(2H,4H)-dione(Compound 51, Example III, Step F) in 5 mL of tetrahydrofuran. Theresulting mixture was stirred at room temperature for one hour.Tetrabutylammonium bromide (0.5 g, 0.002 mole) and potassium hydroxide(0.5 g, 0.009 mole) were added, and the mixture was heated at 60°-70° C.for approximately 1.5 hours. While maintaining the temperature at 60°C., a solution of 0.5 g (0.004 mole) of 1-bromo-2-fluoroethane in 5 mLof tetrahydrofuran was added. After complete addition, the mixture wasallowed to cool to room temperature and was stirred for approximately 18hours. The mixture was partitioned between dilute aqueous hydrochloricacid and ethyl acetate. The organic phase was dried over anhydrousmagnesium sulfate and filtered. Evaporation of the filtrate underreduced pressure produced an oil. The oil was subjected to columnchromatography on silica gel, eluting with ethyl acetate:n-heptane(1:1). Evaporation of the appropriate fractions provided a solid whichwas recrystallized from ethyl acetate:n-heptane to give 0.4 g of2-[2,4-dichloro-5-(1-methylethoxy)phenyl]-4-(2-fluoroethyl)-1,2,4-triazine-3,5(2H,4H)-dione,Compound 26 in the tables.

The nmr spectrum was consistent with the assigned structure.

EXAMPLE IX2-[4-CHLORO-2-FLUORO-5-(3-BROMO-2-PROPYNYLOXY)PHENYL]-4-METHYL-1,2,4-TRIAZINE-3,5(2H,4H)-DIONE

To a stirred mixture of 0.05 g (0.002 mole) of sodium hydride in 5 mL oftetrahydrofuran was added a solution of 0.55 g (0.0018 mole) of2-[4-chloro-2-fluoro-5-(2-propynyloxy)phenyl]-4-methyl-1,2,4-triazine-3,5(2H,4H)-dione(Compound 21, see Example III, Step J) in 5 mL of tetrahydrofuran. Tothis mixture was added a solution of 0.28 g (0.0018 mole) of bromine in5 mL of tetrahydrofuran. After complete addition, the reaction mixturewas stirred at room temperature for one hour. Water, 5 mL, was added tothe mixture, and the total stirred at room temperature for two days. Themixture was partitioned between water and ethyl acetate. The organicphase was dried over anhydrous magnesium sulfate and filtered. Thefiltrate was evaporated under reduced pressure to yield 0.45 g of2-[4-chloro-2-fluoro-5-(3-bromo-2-propynyloxy)phenyl]-4-methyl-1,2,4-triazine-3,5(2H,4H)-dioneas a solid (mp 127°-129° C.), Compound 48 in the tables.

The nmr spectrum was consistent with the assigned structure.

EXAMPLE X METHYL2-[2-CHLORO-4-FLUORO-5-(2,3,4,5-TETRAHYDRO-4-METHYL-3,5-DIOXO-1,2,4-TRIAZIN-2-YL)PHENOXY]-PROPIONATEStep A2-(4-Chloro-2-fluoro-5-hydroxyphenyl)-4-methyl-1,2,4-triazine-3,5(2H,4H)-dione

Treatment of2-[4-chloro-2-fluoro-5-(1-methylethoxy)phenyl]-4-methyl-1,2,4-triazine-3,5(2H,4H)-dione(Compound 18, see Example III G) with sulfuric acid in the manner ofExample III H produced the phenolic compound2-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-methyl-1,2,4-triazine-3,5-(2H,4H)-dione,Compound 30 in the tables.

The nrm spectrum was consistent with the assigned structure.

Step B Methyl2-[2-chloro-4-fluoro-5-(2,3,4,5-tetrahydro-4-methyl-3,5-dioxo-1,2,4-triazin-2-yl)phenoxy]proprionate

Treatment of Compound 30 with methyl 2-chloropropionate in the presenceof potassium carbonate in the manner of Example VI gave methyl2-[2-chloro-4-fluoro-5-(2,3,4,5-tetrahydro-4-methyl-3,5-dioxo-1,2,4-triazin-2-yl)phenoxy]propionate,Compound 42 in the tables.

The nmr spectrum was consistent with the assigned structure.

Compounds 43, 44 and 49 were prepared in a similar manner by treatmentof2-(4-chloro-2-fluoro-5-hydroxyphenyl)-4-methyl-1,2,4-triazine-3,5(2H,4H)-dionewith ethyl chloroacetate, propargyl bromide, and iodoacetamiderespectively.

The nmr and ir spectra were consistent with the assigned structures.

Other compounds of the invention may be prepared by the methodsexemplified above or by methods within the skill of the art.

HERBICIDAL ACTIVITY

The plant test species used in demonstrating the herbicidal activity ofcompounds of this invention include cotton (Gossypium hirsutum var.Stoneville), soybean (Glycine max var. Williams), field corn (Zea maysvar. Agway 595S), wheat (Triticum aestivium var. Prodax), field bindweed(Convolvulus arvensis), morningglory (Ipomea lacunosa or Ipomeahederacea), velvetleaf (Abutilon theophrasti), barnyardgrass(Echinochloa crus galli), green foxtail (Setaria viridis), andjohnsongrass (Sorghum halepense).

Seeds or tubers of the plant test species were planted in furrows insteam sterilized sandy loam soil contained in disposable fiber flats. Atopping soil of equal portions of sand and sandy loam soil was placeduniformly on top of each flat to a depth of approximately 0.5 cm.

The flats for the preemergence test were watered, then drenched with theappropriate amount of a solution of the test compound in a mixture ofacetone and water containing a small amount (up to 0.5% v/v) of sorbitanmonolaurate emulsifier/solubilizer. The concentration of the testcompound in solution was varied to give a range of application rates,generally 8.0 kg/ha and submultiples thereof. The flats were placed in agreenhouse and watered regularly at the soil surface for 21 days atwhich time phytotoxicity data were recorded.

The flats for the postemergence test were placed in a greenhouse andwatered for 8-10 days, then the foliage of the emerged test plants wassprayed with a solution of the test compound in acetone-water containingup to 0.5% sorbitan monolaurate. After spraying the foliage was kept dryfor 24 hours, then watered regularly for 21 days, and phytotoxicity datarecorded.

Phytotoxicity data were taken either as percent kill or percent control.Percent control was determined by a method similar to the 0 to 100rating system disclosed in "Research Methods In Weed Science," 2nd ed.,B. Truelove, Ed.; Southern Weed Science Society; Auburn University,Auburn, Ala., 1977. The present rating system is as follows:

    ______________________________________                                        Herbicide Rating System                                                       Rating                                                                        Per-                                                                          cent  Description                                                             Con-  of Main   Crop           Weed                                           trol  Categories                                                                              Description    Description                                    ______________________________________                                         0    No effect No crop reduction                                                                            No weed control                                                or injury                                                     10              Slight discoloration                                                                         Very poor weed                                                 or stunting    control                                        20    Slight    Some discoloration,                                                                          Poor weed control                                    effect    stunting or stand loss                                        30              Crop injury more                                                                             Poor to deficient                                              pronounced but not                                                                           weed control                                                   lasting                                                       40              Moderate injury,                                                                             Deficient weed                                                 crop usually   control                                                        recovers                                                      50    Moderate  Crop injury more                                                                             Deficient to                                         effect    lasting, recovery                                                                            moderate weed                                                                 control                                        60              Lasting crop   Moderate weed                                                  injury no recovery                                                                           control                                        70              Heavy injury and                                                                             Control somewhat                                               stand loss     less than satis-                                                              factory                                        80    Severe    Crop nearly de-                                                                              Satisfactory to                                      effect    stroyed a few  good weed control                                              survivors                                                     90              Only occasional                                                                              Very good to                                                   live plants left                                                                             excellent control                              100   Complete  Complete crop  Complete weed                                        effect    destruction    destruction                                    ______________________________________                                    

Herbicidal data at selected application rates are given for variouscompounds of the invention in Table 3 and Table 4 below. The testcompounds are identified therein by numbers which correspond to those inTable 1.

In Tables 3 and 4 below:

"kg/ha" is kilograms per hectare,

"% K" is percent kill, and

"%C" is percent control.

It is clear from the data that the generic class of aryltriazinedionesand sulfur analogs thereof described and illustrated herein ischaracterized by herbicidal activity, and that the degree of thisactivity varies among specific compounds within this class and to someextent among the species of plant to which these compounds may beapplied. Thus, selection of a specific herbicidal compound for controlof a specific plant may readily be made.

For herbicidal application, the active compounds as above defined areformulated into herbicidal compositions, by admixture, in herbicidallyeffective amounts, with adjuvants and carriers normally employed in theart for facilitating the dispersion of active ingredients for theparticular utility desired, recognizing the fact that the formulationand mode of application of a toxicant may affect the activity of thematerial in a given application. Thus, for agricultural use the presentherbicidal compounds may be formulated as granules of relatively largeparticle size, as water-soluble or water-dispersible granules, aspowdery dusts, as wettable powders, as emulsifiable concentrates, assolutions, or as any of several other known types of formulations,depending on the desired mode of application.

For preemergence application these herbicidal compositions are usuallyapplied either as sprays, dusts, or granules in the areas in whichsuppression of vegetation is desired. For postemergence control ofestablished plant growth, sprays or dusts are most commonly used. Theseformulations may contain as little as 0.5% to as much as 95% or more byweight of active ingredient.

Dusts are free flowing admixtures of the active ingredient with finelydivided solids such as talc, natural clays, kieselguhr, flours such aswalnut shell and cottonseed flours, and other organic and inorganicsolids which act as dispersants and carriers for the toxicant; thesefinely divided solids have an average particle size of less than about50 microns. A typical dust formulation useful herein is one containing1.0 part of the herbicidal compound and 99.0 parts of talc.

Wettable powders, also useful formulations for both pre- andpostemergence herbicides, are in the form of finely divided particleswhich disperse readily in water or other dispersant. The wettable powderis ultimately applied to the soil either as a dry dust or as an emulsionin water or other liquid. Typical carriers for wettable powders includeFuller's earth, kaolin clays, silicas, and other highly absorbent,readily wet inorganic diluents. Wettable powders normally are preparedto contain about 5-80% of active ingredient, depending on the absorbencyof the carrier, and usually also contain a small amount of a wetting,dispersing or emulsifying agent to facilitate dispersion. For example, auseful wettable powder formulation contains 80.8 parts of the herbicidalcompound, 17.9 parts of Palmetto clay, and 1.0 part of sodiumlignosulfonate and 0.3 part of sulfonated aliphatic polyester as wettingagents. Frequently, additional wetting agent and/or oil will be added tothe tank-mix for postemergence application to facilitate dispersion onthe foliage and absorption by the plant.

Other useful formulations for herbicidal applications are emulsifiableconcentrates. Emulsifiable concentrates are homogeneous liquid or pastecompositions dispersible in water or other dispersant, and may consistentirely of the herbicidal compound and a liquid or solid emulsifyingagent, or may also contain a liquid carrier, such as xylene, heavyaromatic naphthas, isophorone, or other non-volatile organic solvent.For herbicidal application these concentrates are dispersed in water orother liquid carrier, and normally applied as a spray to the area to betreated. The percentage by weight of the essential active ingredient mayvary according to the manner in which the composition is to be applied,but in general comprises 0.5 to 95% of active ingredient by weight ofthe herbicidal composition.

Typical wetting, dispersing, or emulsifying agents used in agriculturalformulations include, for example, the alkyl and alkylaryl sulfonatesand sulfates and their sodium salts, polyhydric alcohols, and othertypes of surface active agents, many of which are available in commerce.The surface active agent, when used, normally comprises 1% to 15% byweight of the herbicidal composition.

Other useful formulations for herbicidal applications include simplesolutions of the active ingredient in a solvent in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene, or other organic solvents. Granularformulations, wherein the toxicant is carried on relatively coarseparticles, are of particular utility for aerial distribution or forpenetration of cover crop canopy. Pressurized sprays, typically aerosolswherein the active ingredient is dispersed in finely divided form as aresult of vaporization of a low boiling dispersant solvent carrier, suchas the Freons, may also be used. Water-soluble or water-dispersiblegranules are also useful formulations for herbicidal application of thepresent compounds. Such granular formulations are free-flowing,non-dusty, and readily water-soluble or water-miscible. The soluble ordispersible granular formulations described in U.S. Pat. No. 3,920,442are useful herein with the present herbicidal compounds.

The active herbicidal compounds of this invention may be formulatedand/or applied with insecticides, fungicides, nematicides, plant growthregulators, fertilizers, or other agricultural chemicals and may be usedas effective soil sterilants as well as selective herbicides inagriculture. In applying an active compound of this invention, whetherformulated alone or with other agricultural chemicals, an effectiveamount and concentration of the active compound is of course employed.

The active herbicidal compounds of this invention may be used incombination with other herbicides, e.g. they may be mixed with, say, anequal or larger amount of a known herbicide such as chloroacetanilideherbicides such as2-chloro-N-(2,6-diethylphenyl)-N-(methoxymethyl)acetamide (alachlor),2-chloro-N(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide(metolachlor), and N-chloroacetyl-N-(2,6-diethylphenyl)glycine(diethatyl-ethyl); benzothiadiazinone herbicides such as3-(1-methylethyl)-(1H)-2,1,3-benzothiadiazin-4-(3H)-one-2,2-dioxide(bentazon); triazine herbicides such as6-chloro-N-ethyl-N-(1-methylethyl)-1,3,5-triazine-2,4-diamine(atrazine), and2-[4-chloro-6-(ethylamino)-1,3,5-triazin-2-yl]amino-2-methylpropanenitrile(cyanazine); dinitrolaniline herbicides such as2,6-dinitro-N,N-dipropyl-4-(trifluoromethyl)benzeneamine (trifluralin);and aryl urea herbicides such asN'-(3,4-dichlorophenyl)-N,N-dimethylurea (diuron) andN,N-dimethyl-N'-[3-(trifluoromethyl)phenyl]urea (fluometuron).

It is apparent that various modifications may be made in the formulationand application of the compounds of this invention without departingfrom the inventive concepts herein as defined in the claims.

                                      TABLE 1                                     __________________________________________________________________________    Representative Compounds                                                       ##STR14##                                                                    (Except where indicated otherwise, W.sup.1 = W.sup.2 = oxygen).               Compound                                                                      Number                                                                              X.sup.1                                                                         X.sup.2                                                                             Z                 R.sup.1 R.sup.2                               __________________________________________________________________________    1     H H     H                 CH.sub.3                                                                              H                                     2     F H     H                 CH.sub.3                                                                              H                                     3     H Cl    H                 CH.sub.2 CHCH.sub.2                                                                   H                                     4     Cl                                                                              Cl    H                 H       CH.sub.3                              5     Cl                                                                              Cl    H                 CH.sub.3                                                                              CH.sub.3                              6     F Cl    H                 H       H                                     7     F Cl    H                 CH.sub.3                                                                              H                                     8.sup.4                                                                             Cl                                                                              Cl    H                 CH.sub.3                                                                              H                                     9     Cl                                                                              Cl    OH                CH.sub.3                                                                              H                                     10    Cl                                                                              Cl    OCH(CH.sub.3).sub.2                                                                             H       CH.sub.3                              11    Cl                                                                              Cl    OCH(CH.sub.3).sub.2                                                                             H       CO.sub.2 H                            12    Cl                                                                              Cl    OCH(CH.sub.3).sub. 2                                                                            CH.sub.3                                                                              H                                     13    Cl                                                                              Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              CH.sub.3                              14    Cl                                                                              Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              CO.sub.2 H                            15    Cl                                                                              Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 CHCH.sub.2                                                                   H                                     16    Cl                                                                              Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 CHCH.sub.2                                                                   CH.sub.3                              17    F Cl    OCH(CH.sub.3).sub.2                                                                             H       H                                     18    F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     19    F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 CHCH.sub.2                                                                   H                                     20    Cl                                                                              Cl    OCH.sub.2 CCH     CH.sub.3                                                                              H                                     21    F Cl    OCH.sub.2 CCH     CH.sub.3                                                                              H                                     22    Cl                                                                              Cl    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                              CH.sub.3                                                                              H                                     23    Cl                                                                              Cl    OSO.sub.2 CH.sub.3                                                                              CH.sub.3                                                                              H                                     24.sup.1                                                                            F Cl    OCH.sub.2 CCH     CH.sub.3                                                                              H                                     25    Cl                                                                              Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 CCH                                                                          H                                     26    Cl                                                                              Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 CH.sub.2 F                                                                   H                                     27    Cl                                                                              Cl    OCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                           CH.sub.3                                                                              H                                     28    Cl                                                                              Cl    OCH.sub.2 CN      CH.sub.3                                                                              H                                     29    Cl                                                                              Cl    OCH(CH.sub.3).sub.2                                                                             C.sub.2 H.sub.5                                                                       H                                     30    F Cl    OH                CH.sub.3                                                                              H                                     31    H Cl    H                 H       CO.sub.2 H                            32    H Cl    OCH.sub.3         H       CO.sub.2 H                            33    H Cl    H                 H       H                                     34    H CH.sub.3                                                                            H                 H       H                                     35    H CH.sub.3                                                                            H                 CH.sub.3                                                                              H                                     36    H Cl    H                 CH.sub.3                                                                              H                                     37    H Cl    OCH.sub.3         H       H                                     38    H OCH.sub.3                                                                           H                 H       H                                     39    H Cl    OCH.sub.3         CH.sub.3                                                                              H                                     40    H OCH.sub.3                                                                           H                 CH.sub.3                                                                              H                                     41    F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 F                                                                            H                                     42    F Cl    OCH(CH.sub.3)CO.sub.2 CH.sub.2                                                                  CH.sub.3                                                                              H                                     43    F Cl    OCH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                              CH.sub.3                                                                              H                                     44    F Cl    OCH.sub.2 CCH     CH.sub.2 F                                                                            H                                     45    F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 CN                                                                           H                                     46    F Cl    NO.sub.2          CH.sub.3                                                                              H                                     47    F Cl    NH.sub.2          CH.sub.3                                                                              H                                     48    F Cl    OCH.sub.2 CCBr    CH.sub.3                                                                              H                                     49    F Cl    OCH.sub.2 CONH.sub.2                                                                            CH.sub.3                                                                              H                                     50    F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 (CH.sub.2).sub.2 F                                                           H                                     51    Cl                                                                              Cl    OCH(CH.sub.3).sub.2                                                                             H       H                                     52    F Cl    OCH.sub.2 CCI     CH.sub.3                                                                              H                                     53    F Br    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     54    F H     OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     55    F CH.sub.3                                                                            OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     56    F CF.sub.3                                                                            OCH.sub.2 CCH     CH.sub.3                                                                              H                                     57    F OC.sub.6 H.sub.5                                                                    OCH.sub.2 CCH     CH.sub.3                                                                              H                                     58    F OCH.sub.2 C.sub.6 H.sub.5                                                           OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     59    F Cl    NHCH.sub.3        CH.sub.3                                                                              H                                     60    F Cl    N(CH.sub.3).sub.2 CH.sub.3                                                                              H                                     61.sup.1                                                                            F Cl    OSO.sub.2 CH.sub.3                                                                              CH.sub.3                                                                              H                                     62    F Cl    CO.sub.2 H        CH.sub.3                                                                              H                                     63    F Cl    CO.sub.2 CH.sub.3 CH.sub.3                                                                              H                                     64    F Cl    CO.sub.2 C.sub.2 H.sub.5                                                                        CH.sub.3                                                                              H                                     65    F Cl    COSCH.sub.3       CH.sub.3                                                                              H                                     66    F Cl    CO.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                            CH.sub.3                                                                              H                                     67    F Cl    CONH.sub.2        CH.sub.3                                                                              H                                     68    F Cl    CONHCH.sub.3      CH.sub.3                                                                              H                                     69    F Cl    CON(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     70    F Cl    CONHCH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.3                                                                              H                                     71    F Cl    CON(CH.sub.3)CH.sub.2 CH.sub.2 OCH.sub.3                                                        CH.sub.3                                                                              H                                     72    F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 CCH                                                                          H                                     73    F Cl    OCH(CH.sub.3).sub.2                                                                             NH.sub.2                                                                              H                                     74    F Cl    OCH.sub.2 CCH     CH.sub.2 CN                                                                           H                                     75    F Cl                                                                                   ##STR15##        CH.sub.3                                                                              H                                     76    F Cl                                                                                   ##STR16##        CH.sub.3                                                                              H                                     77    F Cl    CH.sub.3          CH.sub.3                                                                              H                                     78    F Cl                                                                                   ##STR17##        CH.sub.3                                                                              H                                     79    F Cl    CF.sub.3          CH.sub.3                                                                              H                                     80    F Cl    SH                CH.sub.3                                                                              H                                     81    F Cl    SO.sub.3 H        CH.sub.3                                                                              H                                     82    F Cl    SCH.sub.3         CH.sub.3                                                                              H                                     83    F Cl    SOCH.sub.3        CH.sub.3                                                                              H                                     84    F Cl    SO.sub.2 CH.sub.3 CH.sub.3                                                                              H                                     85    F Cl    SCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     86    F Cl    SCH.sub.2 CCH     CH.sub.3                                                                              H                                     87    F Br    NHCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                          CH.sub.3                                                                              H                                     88    F Cl    NHCH(CH.sub.3)CONHCH.sub.3                                                                      CH.sub.3                                                                              H                                     89    F Cl    NHCH(CH.sub.3).sub.2                                                                            CH.sub.3                                                                              H                                     90    F Cl    NHCH.sub.2 CCH    CH.sub.3                                                                              H                                     91    F Cl                                                                                   ##STR18##        CH.sub.3                                                                              H                                     92    F Cl    NHCOCH.sub.3      CH.sub.3                                                                              H                                     93    F Cl    NHCO.sub.2 CH.sub.3                                                                             CH.sub.3                                                                              H                                     94    F Cl                                                                                   ##STR19##        CH.sub.3                                                                              H                                     95    F Cl    OCF.sub.2 H       CH.sub.3                                                                              H                                     96    F Cl    OCH.sub.2 OCH.sub.3                                                                             CH.sub.3                                                                              H                                     97    F Cl                                                                                   ##STR20##        CH.sub.3                                                                              H                                     98    F Cl                                                                                   ##STR21##        CH.sub.3                                                                              H                                     99    F Cl                                                                                   ##STR22##        CH.sub.3                                                                              H                                     100   F Cl                                                                                   ##STR23##        CH.sub.3                                                                              H                                     101   F Cl                                                                                   ##STR24##        CH.sub.3                                                                              H                                     102   F Cl                                                                                   ##STR25##        CH.sub.3                                                                              H                                     103   F Cl                                                                                   ##STR26##        CH.sub.3                                                                              H                                     104   F Cl                                                                                   ##STR27##        CH.sub.3                                                                              H                                     105   F Cl                                                                                   ##STR28##        CH.sub.3                                                                              H                                     106   F Cl                                                                                   ##STR29##        CH.sub.3                                                                              H                                     107   F Cl    OSO.sub.2 N(CH.sub.3).sub.2                                                                     CH.sub.3                                                                              H                                     108   F Cl    OSO.sub.2 C.sub.6 H.sub.5                                                                       CH.sub.3                                                                              H                                     109   F Cl    OCH.sub.2 CCH     CH.sub.2 (CH.sub.2).sub.2 F                                                           H                                     110   F Cl    OCH.sub.2 CCH     CH.sub.2 SO.sub.2 CH.sub.3                                                            H                                     111   F Cl    OCH.sub.2 CCH     CH.sub.2 CH.sub.2 OCH.sub.3                                                           H                                     112   F Cl    OCH.sub.2 CCH     CH.sub.3                                                                              C.sub.2 H.sub.5                       113   F Cl    OH                H       H                                     114.sup.1                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     115.sup.2                                                                           F Cl    OCH.sub.2 CCH     CH.sub.3                                                                              H                                     116.sup.2                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     117.sup.3                                                                           F Cl    OCH.sub.2 CCH     CH.sub.3                                                                              H                                     118.sup.3                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     119   F Cl    OCH(CH.sub.3).sub. 2                                                                            CH.sub.2 OCH.sub.3                                                                    H                                     120   F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     121   F OCH.sub.3                                                                           OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     122   F Cl                                                                                   ##STR30##        CH.sub.3                                                                              H                                     123   F Cl                                                                                   ##STR31##        CH.sub.3                                                                              H                                     124   F Cl    OCH.sub.2 SCH.sub.3                                                                             CH.sub.3                                                                              H                                     125   F Cl    OCH.sub.2 CHCH.sub.2                                                                            CH.sub.3                                                                              H                                     126   F Cl    OCH.sub.2 C(Cl)CH.sub.2                                                                         CH.sub.3                                                                              H                                     127   F Cl    OCOCH.sub.3       CH.sub.3                                                                              H                                     128   F Cl    OCH.sub.2 CO.sub.2 H                                                                            CH.sub.3                                                                              H                                     129   F Cl    OCH.sub.2 CO.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H                                     130   F Cl                                                                                   ##STR32##        CH.sub.3                                                                              H                                     131   F Cl                                                                                   ##STR33##        CH.sub.3                                                                              H                                     132   F Cl                                                                                   ##STR34##        CH.sub.3                                                                              H                                     133   F Cl                                                                                   ##STR35##        CH.sub.3                                                                              H                                     134   F Cl                                                                                   ##STR36##        CH.sub.3                                                                              H                                     135   F Cl                                                                                   ##STR37##        CH.sub.3                                                                              H                                     136   F Cl                                                                                   ##STR38##        CH.sub.3                                                                              H                                     137   F Cl                                                                                   ##STR39##        CH.sub.3                                                                              H                                     138   F Cl    OCH.sub.2 CONHCH.sub.2 OCH.sub.3                                                                CH.sub.3                                                                              H                                     139   F Cl    OCH.sub.2 CONHCH.sub.2 SCH.sub.3                                                                CH.sub.3                                                                              H                                     140   F Cl    OCH.sub.2 CO.sub.2 CH.sub.2 CF.sub.3                                                            CH.sub.3                                                                              H                                     141   F Cl    OCH(CH.sub.3)CO.sub.2 CH.sub.2CHCl.sub.2                                                        CH.sub.3                                                                              H                                     142   F Cl    OC(CH.sub.3).sub.2 CO.sub.2 CH.sub.2CHCH.sub.2                                                  CH.sub.3                                                                              H                                     143   F Cl                                                                                   ##STR40##        CH.sub.3                                                                              H                                     144   F Cl                                                                                   ##STR41##        CH.sub.3                                                                              H                                     145   F Cl    OCH.sub.2 CO.sub.2 C.sub.6 H.sub.5                                                              CH.sub.3                                                                              H                                     146   F Cl    OCH.sub.2 CO.sub.2 CH.sub. 2 C.sub.6 H.sub.5                                                    CH.sub.3                                                                              H                                     147   F Cl    OCH(CH.sub.3)CO.sub.2 CH.sub.2 CN                                                               CH.sub.3                                                                              H                                     148   F Cl    OCH.sub.2 CO.sub.2 CH.sub.2 CCH                                                                 CH.sub.3                                                                              H                                     149   F Cl    OCH.sub.2 CO.sub.2 NC(CH.sub.3).sub.2                                                           CH.sub.3                                                                              H                                     150   F Cl                                                                                   ##STR42##        CH.sub.3                                                                              H                                     151   F Cl                                                                                   ##STR43##        CH.sub.3                                                                              H                                     152   F Cl                                                                                   ##STR44##        H       H                                     153.sup.1                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             H       H                                     154.sup.2                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             H       H                                     155.sup.3                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             H       H                                     156.sup.1                                                                           F Cl    OCH.sub.2 CCH     H       H                                     157.sup.2                                                                           F Cl    OCH.sub.2 CCH     H       H                                     158.sup.3                                                                           F Cl    OCH.sub.2 CCH     H       H                                     159.sup.1                                                                           F Cl    OH                H       H                                     160.sup.2                                                                           F Cl    OH                H       H                                     161.sup.3                                                                           F Cl    OH                H       H                                     162.sup.1                                                                           F Cl    OH                CH.sub.3                                                                              H                                     163.sup.2                                                                           F Cl    OH                CH.sub.3                                                                              H                                     164.sup.3                                                                           F Cl    OH                CH.sub.3                                                                              H                                     165.sup.1                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             H       CO.sub.2 H                            166.sup.2                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             H       CO.sub.2 H                            167.sup.3                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             H       CO.sub.2 H                            168.sup.1                                                                           F Cl    OCH.sub.2 CCH     H       CO.sub.2 H                            169.sup.2                                                                           F Cl    OCH.sub.2 CCH     H       CO.sub.2 H                            170.sup.3                                                                           F Cl    OCH.sub.2 CCH     H       CO.sub.2 H                            171.sup.1                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              CO.sub.2 H                            172.sup.2                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              CO.sub.2 H                            173.sup.3                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              CO.sub.2 H                            174.sup.1                                                                           F Cl    OCH.sub.2 C CH    CH.sub.3                                                                              CO.sub.2 H                            175.sup.2                                                                           F Cl    OCH.sub.2 CCH     CH.sub.3                                                                              CO.sub.2 H                            176.sup.3                                                                           F Cl    OCH.sub.2 CCH     CH.sub.3                                                                              CO.sub.2 H                            177   F Cl    OCH.sub.2 CCH     H       H                                     178   F Cl    OCH(CH.sub.3).sub.2                                                                             H       CO.sub.2 H                            179   F Cl    OCH.sub.2 CCH     H       CO.sub.2 H                            180   F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              CO.sub.2 H                            181   F Cl    OCH.sub.2 CCH     CH.sub.3                                                                              CO.sub.2 H                            182.sup.1                                                                           F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     183   F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 CH.sub.2 CH.sub.3                                                            H                                     184   F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 CH.sub.2 F                                                                   H                                     185   F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 (CH.sub.2).sub.2 CH.sub.3                                                    H                                     186   Cl                                                                              Cl    NH.sub.2          CH.sub.3                                                                              H                                     187   Cl                                                                              Cl    N(COCH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     188   Cl                                                                              Cl    Cl                CH.sub.3                                                                              H                                     189   F Cl    I                 CH.sub.3                                                                              H                                     190   F Cl    Cl                CH.sub.3                                                                              H                                     191   F Cl    OCSN(CH.sub.2 CH.sub.3).sub.2                                                                   CH.sub.3                                                                              H                                     192   F Cl    SCON(CH.sub.2 CH.sub.3).sub.2                                                                   CH.sub.3                                                                              H                                     193   F Cl    OCH(CH.sub.3)CO.sub.2 C(CH.sub.3).sub.3                                                         CH.sub.3                                                                              H                                     194   F Cl    NHNC(CH.sub.3).sub.2                                                                            CH.sub.3                                                                              H                                     195   F Cl    OCH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                                          CH.sub.3                                                                              H                                     196   F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 SCH.sub.3                                                                    H                                     197   F Cl    OCH(CH.sub.3).sub.2                                                                             CH.sub.2 SOCH.sub.3                                                                   H                                     198   F Cl    OCH(CH.sub.3)CO.sub.2 H                                                                         CH.sub.3                                                                              H                                     199.sup.1                                                                           F Br    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     200   F Cl    O(CH.sub.2).sub.2 CH.sub.3                                                                      CH.sub.3                                                                              H                                     201   F Cl    O(CH.sub.2).sub.2 CHCH.sub.2                                                                    CH.sub.3                                                                              H                                     202   F Cl    OCH.sub.2 CN      CH.sub.3                                                                              H                                     203.sup.1                                                                           F Br    OCH.sub.2 CCH     CH.sub.3                                                                              H                                     204.sup.2                                                                           F Br    OCH.sub.2 CCH     CH.sub.3                                                                              H                                     205.sup.3                                                                           F Br    OCH.sub.2 CCH     CH.sub.3                                                                              H                                     206   F Cl                                                                                   ##STR45##        CH.sub.3                                                                              H                                     207   F Cl    OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                        CH.sub.3                                                                              H                                     208   F Cl    OCH(CH.sub.3)COSC.sub.2 H.sub.5                                                                 CH.sub.3                                                                              H                                     209   F Cl                                                                                   ##STR46##        CH.sub.3                                                                              H                                     210   F Cl                                                                                   ##STR47##        CH.sub.3                                                                              H                                     211   F Cl    OCH.sub.3         CH.sub.3                                                                              H                                     212   F Cl    OCH.sub.2 SOCH.sub.3                                                                            CH.sub.3                                                                              H                                     213   F Cl    OCH.sub.2 SO.sub.2 CH.sub.3                                                                     CH.sub.3                                                                              H                                     214   F Cl    F                 H       H                                     215   F Cl    F                 CH.sub.3                                                                              H                                     216.sup.2                                                                           F Br    OCH(CH.sub.3).sub.2                                                                             CH.sub.3                                                                              H                                     217.sup.3                                                                           F Br    OCH(CH.sub.3).sub. 2                                                                            CH.sub.3                                                                              H                                     218   F Cl    SO.sub.2 Cl       CH.sub.3                                                                              H                                     219   F Cl                                                                                   ##STR48##        CH.sub.3                                                                              H                                     220   F Cl    OCH(OC.sub.2 H.sub.5)CO.sub.2 C.sub.2 H.sub.5                                                   CH.sub.3                                                                              H                                     221   F Cl    OCH(OCH.sub.3)CO.sub.2 CH.sub.3                                                                 CH.sub.3                                                                              H                                     222   F Cl                                                                                   ##STR49##        CH.sub.3                                                                              H                                     223   F Cl    SCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                        CH.sub.3                                                                              H                                     224   F Cl                                                                                   ##STR50##        CH.sub.3                                                                              H                                     225   F Cl    SCH.sub.2 OCH.sub.3                                                                             CH.sub.3                                                                              H                                     226   F Cl    SCH.sub.2 CN      CH.sub.3                                                                              H                                     227   F Br    OCH.sub.2 CCH     CH.sub.3                                                                              H                                     228   F Cl                                                                                   ##STR51##        CH.sub.3                                                                              H                                     229   F Cl    OCH.sub.2 Si(CH.sub.3).sub.3                                                                    CH.sub.3                                                                              H                                     230   F Cl    OC.sub.2 H.sub.5  CH.sub.3                                                                              H                                     231   F Cl                                                                                   ##STR52##        CH.sub.3                                                                              H                                     232   F Cl    NHCH(CH.sub.3)CO.sub.2 C.sub.2 H.sub.5                                                          CH.sub.3                                                                              H                                     233   F Br    OCH(CH.sub.3)CO.sub.2 CH(CH.sub.3).sub.2                                                        CH.sub.3                                                                              H                                     234   F Br    OCH.sub.2 OCH.sub.3                                                                             CH.sub.3                                                                              H                                     235   F Br                                                                                   ##STR53##        CH.sub.3                                                                              H                                     236   F Cl    O(CH.sub.2).sub.2 F                                                                             CH.sub.3                                                                              H                                     237   F Cl    OCH.sub.2 CF.sub.3                                                                              CH.sub.3                                                                              H                                     238   F Cl                                                                                   ##STR54##        CH.sub.3                                                                              H                                     239   F Cl    OCH.sub.2 CCH     CHF.sub.3                                                                             H                                     240   F Br    H                 CH.sub.3                                                                              H                                     241.sup.1                                                                           F Br    H                 CH.sub.3                                                                              H                                     242.sup.2                                                                           F Cl    H                 CH.sub.3                                                                              H                                     243   F Cl    OC(CH.sub.3).sub.2 CO.sub.2 C.sub.2 H.sub.5                                                     CH.sub.3                                                                              H                                     244   F Cl                                                                                   ##STR55##        CH.sub.3                                                                              H                                     245   F Cl    CN                CH.sub.3                                                                              H                                     246   F Cl    CH.sub.3          CH.sub.3                                                                              H                                     247   F Cl    CF.sub.3          CH.sub.3                                                                              H                                     248   F Cl    CO.sub.2 Na       CH.sub.3                                                                              H                                     249   F Cl    SO.sub.3 Na       CH.sub.3                                                                              H                                     250   F Br    OCH(CH.sub.3)CO.sub.2 Na                                                                        CH.sub.3                                                                              H                                     251   F Cl                                                                                   ##STR56##        CH.sub.3                                                                              H                                     252   F Cl                                                                                   ##STR57##        CH.sub.3                                                                              H                                     253   F Cl                                                                                   ##STR58##        CH.sub.3                                                                              H                                     254   F Cl                                                                                   ##STR59##        CH.sub.3                                                                              H                                     255   F Br                                                                                   ##STR60##        CH.sub.3                                                                              H                                     256   F CF.sub.3                                                                             ##STR61##        CH.sub.3                                                                              H                                     __________________________________________________________________________     .sup.1 W.sup.1 = O, W.sup.2 = S                                               .sup.2 W.sup.1 = S, W.sup.2 = O                                               .sup.3 W.sup.1 = W.sup.2 = S                                                  .sup.4 X.sup.1 = 3Cl                                                     

                  TABLE 2                                                         ______________________________________                                        Characterizing Data                                                           Com-                                                                          pound                                                                         Num-  M.P.                Elemental Analysis                                  ber   (°C.)                                                                           Empirical Formula                                                                              C    H    N                                   ______________________________________                                        1     79-81    C.sub.10 H.sub.9 N.sub.3 O.sub.2                               2     oil      C.sub.10 H.sub.8 FN.sub.3 O.sub.2 /                                                          C   53.22                                                                              3.80 18.62                                            0.25 H.sub.2 O F   53.55                                                                              3.48 18.09                             3     99-100   C.sub.12 H.sub.10 CIN.sub.3 O.sub.2                                                          C   54.66                                                                              3.82 15.94                                                           F   54.63                                                                              3.57 16.15                             4     197(d)   C.sub.10 H.sub.7 Cl.sub.2 N.sub.3 O.sub.2                      5     109-110  C.sub.11 H.sub.9 Cl.sub.2 N.sub.3 O.sub.2                      6     202-203  C.sub.9 H.sub.5 ClFN.sub.3 O.sub.2                             7     114-116  C.sub.10 H.sub.7 ClFN.sub.3 O.sub.2                            8     167-168  C.sub.10 H.sub.7 Cl.sub.2 N.sub.3 O.sub.2                                                    C   44.14                                                                              2.59 15.44                                                           F   43.85                                                                              2.40 15.22                             9     199-201  C.sub.10 H.sub.7 Cl.sub.2 N.sub.3 O.sub.3                      10    163-164  C.sub.13 H.sub.13 Cl.sub.2 N.sub.3 O.sub.3                                                   C   47.29                                                                              3.97 12.73                                                           F   47.47                                                                              3.82 12.33                             11    195-197  C.sub.13 H.sub.11 Cl.sub.2 N.sub.3 O.sub.5 /                                                 C   42.30                                                                              3.28 11.38                                   (d)      0.5 H.sub.2 O  F   42.38                                                                              3.31 11.75                             12    111-112  C.sub.13 H.sub.13 Cl.sub.2 N.sub.3 O.sub.3                                                   C   47.29                                                                              3.97 12.73                                                           F   47.18                                                                              4.03 12.43                             13    oily solid                                                                             C.sub.14 H.sub.15 Cl.sub.2 N.sub.3 O.sub.3                     14    230(d)   C.sub.14 H.sub.13 Cl.sub.2 N.sub.3 O.sub.3                     15    103-104  C.sub.15 H.sub.15 Cl.sub.2 N.sub.3 O.sub.3                                                   C   50.58                                                                              4.24 11.80                                                           F   50.30                                                                              4.25 11.52                             16    74-75    C.sub.16 H.sub.17 Cl.sub.2 N.sub.3 O.sub.3                     17    oil      C.sub.12 H.sub.11 ClFN.sub.3 O.sub.3                           18    82-84    C.sub.13 H.sub.13 ClFN.sub.3 O.sub.3                           19    84-86    C.sub.15 H.sub.15 ClFN.sub.3 O.sub.3                           20    119-120  C.sub.13 H.sub.9 Cl.sub.2 N.sub.3 O.sub.3                      21    122-123  C.sub.13 H.sub.9 ClFN.sub.3 O.sub.3                            22    115-117  C.sub.14 H.sub.13 Cl.sub.2 N.sub. 3 O.sub.5                    23    oil      C.sub.11 H.sub.9 Cl.sub.2 N.sub.3 O.sub.5 S                                                  C   36.08                                                                              2.48 11.48                                                           F   36.99                                                                              2.70 10.85                             24    134-135  C.sub.13 H.sub.9 ClFN.sub.3 O.sub.3 S                          25    142-144  C.sub.15 H.sub.13 Cl.sub.2 N.sub.3 O.sub.2                                                   C   50.87                                                                              3.70 11.86                                                           F   50.37                                                                              3.95 11.66                             26    oil      C.sub.13 H.sub.14 Cl.sub.2 FN.sub.3 O.sub.3                                                  C   46.43                                                                              3.90 11.60                                                           F   46.45                                                                              3.66 11.48                             27    108-110  C.sub.15 H.sub.15 Cl.sub.2 N.sub.3 O.sub.5                                                   C   46.41                                                                              3.89 10.82                                                           F   46.14                                                                              3.70 10.65                             28    169-170  C.sub.12 H.sub.8 Cl.sub.2 N.sub.4 O.sub.3                                                    C   43.46                                                                              2.58 16.95                                                           F   43.27                                                                              2.36 16.69                             29    82-83    C.sub.14 H.sub.15 Cl.sub.2 N.sub.3 O.sub.3                                                   C   48.86                                                                              4.39 12.21                                                           F   49.25                                                                              4.22 12.15                             30    183(d)   C.sub.10 H.sub.7 ClFN.sub.3 O.sub.3                            31    155(d)   C.sub.10 H.sub.6 ClN.sub.3 O.sub.4                             32    157(d)   C.sub.11 H.sub.8 ClN.sub.3 O.sub.5                                                           C   48.34                                                                              2.70 18.79                                                           F   48.32                                                                              2.81 18.51                             33    229-230  C.sub.9 H.sub.6 ClN.sub.3 O.sub.2                                                            C   57.82                                                                              4.61 20.23                                                           F   58.11                                                                              4.50 19.73                             34    200-202  C.sub.10 H.sub.9 N.sub.3 O.sub.2 /                                                           C   60.82                                                                              5.10 19.34                                            0.25 H.sub.2 O F   61.35                                                                              5.40 19.85                             35    136-137  C.sub.11 H.sub.11 N.sub.3 O.sub.2                                                            C   50.54                                                                              3.39 17.68                                                           F   50.70                                                                              3.66 17.92                             36    152-154  C.sub.10 H.sub.8 ClN.sub.3 O.sub.2                                                           C   43.48                                                                              3.83 15.22                                                           F   43.61                                                                              3.28 13.10                             37    170-173  C.sub.10 H.sub.8 ClN.sub.3 O.sub.3 /                                                         C   50.63                                                                              4.67 17.71                                            1.25 H.sub.2 O F   50.12                                                                              3.85 16.14                             38    192(d)   C.sub.10 H.sub.9 N.sub.3 O.sub.3 /H.sub.2 O                                                  C   48.54                                                                              3.89 15.44                                                           F   48.47                                                                              3.71 14.10                             39    108-110  C.sub.11 H.sub.10 ClN.sub.3 O.sub.3 /                                                        C   56.65                                                                              4.75 18.01                                            0.25 H.sub.2 O F   56.26                                                                              4.55 17.66                             40    114-116  C.sub.11 H.sub.11 N.sub.3 O.sub.3                                                            C   47.07                                                                              3.65 12.67                                                           F   47.20                                                                              3.77 12.22                             41    111-113  C.sub.13 H.sub. 12 ClF.sub.2 N.sub.3 O.sub.3                                                 C   47.01                                                                              3.66 11.75                                                           F   46.51                                                                              3.69 11.31                             42    100-102  C.sub.14 H.sub.13 ClFN.sub.3 O.sub.5                           43    oil      C.sub.14 H.sub.13 ClFN.sub.3 O.sub.5                           44    oil      C.sub.13 H.sub.8 ClF.sub.2 N.sub.3 O.sub.3                                                   C   47.65                                                                              2.46 12.82                                                           F   48.10                                                                              2.58 12.03                             45    oil      C.sub.14 H.sub.12 ClFN.sub.4 O.sub.3                                                         C   49.64                                                                              3.57 16.54                                                           F   49.44                                                                              3.90 14.65                             46    132-134  C.sub.10 H.sub.6 ClFN.sub.4 O.sub.4                                                          C   39.95                                                                              2.01 18.64                                                           F   40.22                                                                              1.98 18.51                             47    150-152  C.sub.10 H.sub.8 ClFN.sub.4 O.sub.2                                                          C   44.38                                                                              2.98 20.70                                                           F   44.30                                                                              3.29 20.40                             48    127-129  C.sub.13 H.sub.8 BrClFN.sub.3 O.sub.3                          49    208(d)   C.sub.12 H.sub.10 ClFN.sub.4 O.sub.4                           50    70-71    C.sub.15 H.sub.16 ClF.sub.2 N.sub.3 O.sub.3                                                  C   50.08                                                                              4.48 11.68                                                           F   50.26                                                                              4.45 12.00                             53    89-92    C.sub.13 H.sub.13 BrFN.sub.3 O.sub.3                                                         C   43.59                                                                              3.66 11.73                                                           F   43.47                                                                              3.40 11.72                             55    oil      C.sub.14 H.sub.16 FN.sub.3 O.sub.3                             74    oil      C.sub.14 H.sub.8 ClFN.sub.4 O.sub.3                            75    194-197  C.sub.17 H.sub.21 ClFN.sub.5 O.sub.3                           76    155-156  C.sub.17 H.sub.20 ClFN.sub.4 O.sub.4                                                         C   51.20                                                                              5.05 14.05                                                           F   51.20                                                                              5.19 14.22                             77    138-139  C.sub.11 H.sub.9 ClFN.sub.3 O.sub.2                                                          C   40.99                                                                              3.36 15.58                                                           F   40.88                                                                              2.90 13.65                             78    122-123  C.sub.15 H.sub.15 ClFN.sub.3 O.sub.3                           82    128-131  C.sub.11 H.sub.9 ClFN.sub.3 O.sub.2 S                          85    95-97    C.sub.13 H.sub.13 ClFN.sub.3 O.sub.2 S                         86    foam     C.sub.13 H.sub.9 ClFN.sub.3 O.sub.2 S                          89    solid    C.sub.13 H.sub.14 ClFN.sub.4 O.sub.2                                                         C   49.93                                                                              4.51 17.92                                                           F   50.55                                                                              4.55 17.31                             96    109-111  C.sub.12 H.sub.11 ClFN.sub.3 O.sub.4                                                         C   45.66                                                                              3.51 13.31                                                           F   45.45                                                                              3.35 12.92                             113   >225     C.sub.9 H.sub.5 ClFN.sub.3 O.sub.3                                                           C   41.96                                                                              1.96 16.31                                                           F   43.20                                                                              2.54 14.69                             114   80-81    C.sub.13 H.sub.12 ClFN.sub.3 O.sub.2 S                                                       C   47.35                                                                              3.97 12.74                                                           F   47.71                                                                              4.05 12.69                             119   100-102  C.sub.14 H.sub.15 ClFN.sub.3 O.sub.4                                                         C   48.92                                                                              4.40 12.22                                                           F   49.09                                                                              4.32 11.95                             124   oil      C.sub.12 H.sub.11 ClFN.sub.3 O.sub.3 S                                                       C   43.46                                                                              3.34 12.67                                                           F   43.89                                                                              3.46 12.12                             125   oil      C.sub.13 H.sub.11 ClFN.sub.3 O.sub.3                                                         C   50.09                                                                              3.56 13.48                                                           F   50.16                                                                              3.73 13.00                             182   134-135  C.sub.13 H.sub.9 ClFN.sub.3 O.sub.2 S                          183   61-63    C.sub.15 H.sub.17 ClFN.sub.3 O.sub.3                                                         C   52.72                                                                              5.01 12.29                                                           F   52.55                                                                              4.95 11.53                             184   oil      C.sub.14 H.sub.14 ClF.sub.2 N.sub.3 O.sub.3                                                  C   48.64                                                                              4.08 12.15                                                           F   47.88                                                                              3.81 11.68                             185   73-74    C.sub.16 H.sub.19 ClFN.sub.3 O.sub.3                                                         C   54.01                                                                              5.38 11.81                                                           F   54.55                                                                              5.59 11.40                             186   168-171  C.sub.10 H.sub.8 Cl.sub.2 N.sub.4 O.sub.2                      187   foam     C.sub.14 H.sub.12 Cl.sub.2 N.sub.4 O.sub.4 /                                                 C   44.23                                                                              3.45 14.73                                            0.5 H.sub.2 O  F   44.15                                                                              3.15 14.44                             188   172-173  C.sub.10 H.sub.6 Cl.sub.3 N.sub.3 O.sub.2                                                    C   39.18                                                                              1.97 13.71                                                           F   39.83                                                                              2.35 13.55                             189   182-185  C.sub.10 H.sub.6 ClFIN.sub.3 O.sub.2                                                         C   31.48                                                                              1.59 11.01                                                           F   33.48                                                                              1.83 11.59                             190   140-142  C.sub.10 H.sub.6 Cl.sub.2 FN.sub.3 O.sub.2                                                   C   41.41                                                                              2.08 14.49                                                           F   41.65                                                                              2.13 14.05                             191   120-121  C.sub.15 H.sub.16 ClFN.sub.4 O.sub.3 S                                                       C   46.57                                                                              4.17 14.48                                                           F   46.47                                                                              4.02 14.29                             192   156-157  C.sub.15 H.sub.16 ClFN.sub.4 O.sub.3 S                                                       C   46.57                                                                              4.17 14.48                                                           F   46.66                                                                              4.14 14.37                             193   86-88    C.sub.17 H.sub.19 ClFN.sub.3 O.sub.4                                                         C   50.94                                                                              5.03 10.48                                                           F   51.13                                                                              4.75 10.35                             194   146-147  C.sub.13 H.sub.13 ClFN.sub.5 O.sub.2                                                         C   47.94                                                                              4.02 21.50                                                           F   48.20                                                                              3.77 21.46                             195   oil      C.sub.14 H.sub.15 ClFN.sub.3 O.sub.5 /                                                       C   45.60                                                                              4.37 11.39                                            0.5 H.sub.2 O  F   45.67                                                                              4.07 11.20                             196   95-97    C.sub.14 H.sub.15 ClFN.sub.3 O.sub.3 S                                                       C   46.73                                                                              4.20 11.68                                                           F   46.76                                                                              4.24 11.39                             197   138-140  C.sub.14 H.sub.15 ClFN.sub.3 O.sub.4 S                                                       C   44.74                                                                              4.02 11.18                                                           F   44.15                                                                              3.78 10.99                             198   123-125  C.sub.13 H.sub.11 ClFN.sub.3 O.sub.5                                                         C   45.43                                                                              3.23 12.23                                                           F   45.14                                                                              3.23 11.95                             200   88-89    C.sub.13 H.sub.13 ClFN.sub.3 O.sub.3                                                         C   49.77                                                                              4.18 13.39                                                           F   49.74                                                                              4.07 13.34                             201   oil      C.sub.14 H.sub.13 ClFN.sub.3 O.sub.3                                                         C   51.62                                                                              4.02 12.90                                                           F   51.32                                                                              4.04 12.50                             202   153-155  C.sub.12 H.sub.8 ClFN.sub.4 O.sub.3                                                          C   46.39                                                                              2.60 18.03                                                           F   46.08                                                                              2.49 17.81                             206   gum      C.sub.16 H.sub.18 ClFN.sub.4 O.sub.2                                                         C   54.47                                                                              5.14 15.83                                                           F   55.83                                                                              4.80 15.36                             207   oil      C.sub.16 H.sub.17 ClFN.sub.3 O.sub.5                                                         C   49.82                                                                              4.44 10.89                                                           F   47.82                                                                              4.31 10.22                             208   oil      C.sub.15 H.sub.15 ClFN.sub.3 O.sub.4 S                                                       C   44.75                                                                              4.02 11.18                                                           F   44.72                                                                              3.71 10.06                             209   97(d)    C.sub.19 H.sub.15 Cl.sub. 2 FN.sub.4 O.sub.6 S/                                              C   42.63                                                                              3.20 10.46                                            H.sub.2 O      F   42.61                                                                              4.06 9.44                              210   solid    C.sub.19 H.sub.15 Cl.sub.2 FN.sub.4 O.sub.6 S/                                               C   42.63                                                                              3.20 10.46                                            H.sub.2 O      F   42.73                                                                              4.27 9.33                              211   145-146  C.sub.11 H.sub.9 ClFN.sub.3 O.sub.3                                                          C   46.25                                                                              3.18 14.71                                                           F   45.90                                                                              2.80 14.46                             212   164-166  C.sub.12 H.sub.11 ClFN.sub.3 O.sub.4 S                                                       C   41.45                                                                              3.19 12.08                                                           F   41.45                                                                              3.07 11.67                             213   154-156  C.sub.12 H.sub.11 ClFN.sub.3 O.sub.5 S                                                       C   39.62                                                                              3.05 11.55                                                           F   39.30                                                                              3.15 11.13                             214   233-234  C.sub.9 H.sub.4 ClF.sub.2 N.sub.3 O.sub.2                                                    C   41.64                                                                              1.55 16.19                                                           F   41.50                                                                              1.78 15.76                             215   110-111  C.sub.10 H.sub.6 ClF.sub.2 N.sub.3 O.sub.2                                                   C   43.90                                                                              2.21 15.36                                                           F   43.64                                                                              2.13 15.21                             218   123-125  C.sub.10 H.sub.6 Cl.sub.2 FN.sub.3 O.sub.4 S                                                 C   33.92                                                                              1.71 11.87                                                           F   34.11                                                                              1.79 11.78                             219   solid    C.sub.19 H.sub.14 Cl.sub.2 FN.sub.3 O.sub.4 S                  220   oil      C.sub.16 H.sub.17 ClFN.sub.3 O.sub.6                                                         C   47.83                                                                              4.27 10.46                                                           F   47.93                                                                              4.13 10.18                             221   oil      C.sub.14 H.sub.13 ClFN.sub.3 O.sub.6                           222   110(d)   C.sub.19 H.sub.15 Cl.sub.2 FN.sub.4 O.sub.5 S.sub.2            223   oil      C.sub.16 H.sub.17 ClFN.sub.3 O.sub.4 S                                                       C   47.82                                                                              4.26 10.46                                                           F   46.14                                                                              4.10 10.04                             224   51-53    C.sub.15 H.sub.15 ClFN.sub.3 O.sub.2 S                         225   95-98    C.sub.12 H.sub.11 ClFN.sub.3 O.sub.2 S                         226   123-125  C.sub.12 H.sub.8 ClFN.sub.4 O.sub.2 S                          227   123-124  C.sub.13 H.sub.9 BrFN.sub.3 O.sub.3                                                          C   44.09                                                                              2.56 11.87                                                           F   44.40                                                                              2.35 11.42                             228   195-196  C.sub.20 H.sub.18 ClFN.sub.4 O.sub.7 S                                                       C   46.83                                                                              3.53 10.92                                                           F   46.94                                                                              3.80 10.39                             229   125-126  C.sub.14 H.sub.17 ClFN.sub.3 O.sub.3 Si                                                      C   46.99                                                                              4.79 11.74                                                           F   47.26                                                                              4.62 11.65                             230   solid    C.sub.12 H.sub.11 ClFN.sub.3 O.sub.3                           231   solid    C.sub.21 H.sub.18 ClFN.sub.4 O.sub.8 S                                                       C   46.72                                                                              3.17 10.38                                                           F   44.35                                                                              3.72 7.43                              232   oil      C.sub.15 H.sub.16 ClFN.sub.4 O.sub.4 /                                                       C   45.29                                                                              4.81 14.08                                            1.5 H.sub.2 O  F   45.40                                                                              4.63 13.65                             233   gum      C.sub.16 H.sub.17 BrFN.sub.3 O.sub.3                                                         C   44.67                                                                              3.98 9.77                                                            F   44.35                                                                              3.93 9.44                              234   79-81    C.sub.12 H.sub.11 BrFN.sub.3 O.sub.4                                                         C   40.02                                                                              3.08 11.68                                                           F   39.86                                                                              2.91 11.29                             235   120(d)   C.sub.19 H.sub.15 BrClFN.sub.4 O.sub.6 S/                                                    C   39.36                                                                              2.96 9.66                                             H.sub.2 O      F   39.62                                                                              2.78 8.49                              236   134-136  C.sub.12 H.sub.10 ClF.sub.2 N.sub.3 O.sub.3                                                  C   45.37                                                                              3.17 13.23                                                           F   44.88                                                                              2.86 12.87                             237   gum      C.sub.12 H.sub.8 ClF.sub.4 N.sub.3 O.sub.3                                                   C   40.75                                                                              2.28 11.88                                                           F   40.51                                                                              2.26 11.16                             ______________________________________                                    

    TABLE 3      Preemergence Herbicidal Activity       Compound No. 1 2 3 4 5 6 7 8 9 10 11 12 13  15 16 17 18 19 20 21 22 23 2     4 25 26 27 28 29 30 Rate (kg/ha) 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0     8.0 8.0 4.0 8.0 8.0 8.0 8.0 8.0 8.0 2.0 8.0 8.0 0.5 8.0 8.0 4.0 4.0 8.0     8.0 Species % K % C % K % C % C % C % C % K % K % K % K % K % K % K % K     % K % C % C % C % C % C % C % C % C % C % C % C % C % C       Cotton 0 90 90 0 0 10 100 0 20 0 0 10 0 0 0 0 100 80 100 100 100 90     100 0 20 90 50 60 100 Soybean 0 90 90 0 0 50 100 0 0 0 0 100 40 10 0 10     100 90 100 100 100 90 100 0 40 30 50 90 100 Field Corn 0 70 100 0 0 50     100 0 0 0 0 70 60 0 0 33 100 100 100 100 90 100 100 0 90 80 100 90 100     Wheat 0 80 100 0 0 50 100 10 10 0 0 100 40 20 0 0 100 100 100 100 0 100     100 20 90 30 70 60 100 Field Bindweed 0 90 100 0 0 50 100 20 0 0 0 100     50 0 100 0 100 100 100 100 100 80 100 0 70 100 10 90 100 Morningglory 30     90 90 0 0 30 100 50 10 0 0 100 0 0 80 0 100 100 100 100 70 90 90 20 50     40 50 70 100 Velvetleaf -- 90 -- 0 0 100 100 -- 0 100 0 100 100 100 0 --     100 -- 100 100 90 100 100 0 100 100 100 100 100 Barnyardgrass 0 90 100 0     0 20 100 80 10 0 0 100 100 30 0 0 100 100 100 100 90 100 100 80 80 100     100 100 100 Green Foxtail 0 100 -- 0 0 90 100 -- --  100 0 100 -- 100 95     -- -- -- 100 100 90 100 100 90 100 100 100 100 100 Johnsongrass 30 80     100 0 0 80 100 90 10 0 0 100 100 30 0 0 100 100 100 100 80 100 100 80 90     100 80 100 100       Compound No. 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49     50 53 55 73 75 76 77 78 82 85 Rate (kg/ha) 8.0 8.0 8.0 8.0 8.0 4.0 8.0     8.0 8.0 8.0 0.5 1.0 1.0 0.5 4.0 4.0 4.0 0.25 2.0 2.0 0.25 0.5 4.0 1.0     1.0 1.0 1.0 2.0 0.5 Species % C % C % C % C % C % C % C % C % C % C % C     % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C %     C    Cotton 0 0 40 0 90 90 0 0 20 90 50 100 40 100 100 10 10 0 100 80 0     30 40 100 90 100 30 100 30 Soybean 0 0 40 0 80 90 70 0 50 90 90 100 70     100 100 90 100 0 100 50 10 20 50 100 80 100 100 100 30 Field Corn 0 0 30     0 80 100 20 0 60 100 90 30 60 100 100 10 30 50 100 90 95 90 40 100 100     100 80 100 90 Wheat 0 0 0 0 70 100 0 0 10 90 100 60 0 100 100 10 30 0 20     100 100 0 90 100 90 90 70 95 30 Field Bindweed 0 0 0 0 40 100 0 0 0 90     80 100 100 100 100 0 20 0 100 40 80 30 100 100 90 10040 9520 Morningglory      0 0 0 0 80 100 0 0 90 80 90 100 100 100 100 10 40 0 100 100 100 20 100     100 90 100 50 100 20 Velvetleaf 0 0 0 0 100 100 0 0 90 100 100 100 100     100 100 100 100 100 100 100 95 100 100 100 100 100 100 100 100 Barnyardgr     ass 0 0 0 0 90 100 0 0 50 100 100 100 100 100 100 0 70 80 100 100 100 30     100 100 90 100 100 100 80 Green Foxtail 0 0 0 0 90 100 0 0 80 100 100     100 100 100 100 90 60 90 100 100 100 40 100 100 100 100 100 100 95     Johnsongrass 0 0 0 0 80 100 0 0 20 100 100 100 90 100 100 10 70 60 100     100 95 20 90 100 100 100 100 100 40       Compound No. 86 89 96 113 114 119 124 125 182 183 184 185 186 187 188     189 190 191 192 193 194 195 196 197 198 200 201 202 206 Rate (kg/ha)     0.125 0.5 0.5 8.0 1.0 0.5 0.5 1.0 0.5 0.5 0.5 0.5 4.0 4.0 2.0 1.0 1.0     8.0 8.0 8.0 4.0 0.5 2.0 4.0 1.0 1.0 1.0 1.0 4.0 Species % C % C % C % C     % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C     % C % C % C % C % C % C % C       Cotton 20 70 70 0 40 10 100 90 100 0 10 10 10 30 20 30 40 60 90 100     100 80 20 50 100 60 50 90 30 Soybean 20 80 70 50 80 50 100 100 100 0 30     0 10 20 10 30 30 60 60 100 100 70 20 50 95 50 50 90 70 Field Corn 90 95     100 20 100 80 100 100 100 20 100 10 10 20 20 40 90 70 100 100 100 100 90     100 50 100 100 90 95 Wheat 40 95 100 10 100 20 100 100 100 30 60 0 0 20     0 30 40 40 60 100 100 70 30 80 80 90 80 50 80 Field Bindweed 20 80 100     10 70 20 100 100 100 30 30 0 0 0 10 30 20 80 100 100 100 80 10 60 90 70     80 100 100 Morningglory 30 40 100 10 90 30 100 100 90 0 30 10 0 20 20 20     30 60 80 100 100 100 20 40 100 100 50 100 80 Velvetleaf 100 100 100 20     100 100 100 100 100 80 90 10 80 40 80 100 100 100 100 100 100 100 80 100     100 100 100 100 100 Barnyardgrass 95 95 100 60 100 40 100 100 100 80 90     20 20 10 0 100 100 100 100 100 100 100 100 50 100 100 100 100 80 Green     Foxtail 90 100 100 20 100 70 100 100 100 90 100 20 0 10 100 100 100 100     100 100 100 100 100 90 100 100 100 100 100 Johnsongrass 60 100 90 30 100     70 100 100 100 90 90 0 0 10 30 90 100 100 100 100 100 90 90 90 95 100 90     90 100       Compound No. 207 208 209 210 211 212 213 214 215 218 219 220 221 222     223 224 225 226 227  228 229 230 231 232 233 234 Rate (kg/ha) 1.0 1.0     1.0 1.0 2.0 2.0 4.0 8.0 4.0 8.0 1.0 2.0 2.0 1.0 1.0 1.0 0.25 2.0 0.125     0.5 4.0 2.0 0.5 2.0 0.5 0.125 Species % C % C % C % C % C % C % C % C %     C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C %     C      Cotton 100 100 95 100 100 100 100 10 100 20 20 30 70 70 100 30 10     100 50 90 20 90 80 100 70 80 Soybean 100 100 80 70 95 100 100 50 100 0     30 90 95 40 100 70 20 100 30 95 30 95 70 100 95 10 Field Corn 70 80 10     20 100 100 100 50 100 20 30 70 70 30 95 80 95 100 100 0 80 100 10 40 40     95 Wheat 90 80 30 60 100 100 100 30 100 10 20 0 30 10 70 20 90 100 100     30 50 100 20 90 60 100 Field Bindweed 100 100 100 100 100 100 100 90 100     50 30 30 100 90 90 20 80 90 95 100 80 100 100 100 100 100 Morningglory     80 100 100 95 100 100 100 70 100 20 50 95 100 100 100 90 100 100 70 100     95 95 90 60 95 100 Velvetleaf 100 100 100 100 100 100 100 100 100 100     100 80 80 100 100 100 100 100 100 100 100 100 100 100 100 100 Barnyardgra     ss 100 100 100 70 100 100 100 20 100 30 90 90 95 0 95 100 100 100 100 70     90 100 20 70 100 100 Green Foxtail 100 100 95 80 100 100 100 100 100 100     100 90 100 0 100 100 90 100 100 95 100 100 30 100 100 100 Johnsongrass     100 95 90 70 100 100 100 60 100 90 60 70 95 0 95 80 40 100 100 100 95     100 70 30 80 100

    TABLE 4      Postemergence Herbicidal Activity       Compound No. 1 2 3 4 5 6 7 8 9 10 11 12 13 15 16 17 18 19 20  21 22 23 2     4 25 26 27 28 29 Rate (kg/ha) 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0     8.0 8.0 4.0 8.0 8.0 8.0 8.0 8.0 8.0 0.25 8.0 8.0 0.5 8.0 8.0 8.0 8.0 8.0     Species % K % C % K % C % C % C % C % K % K % K % K % K % K % K % K % K     % K % K % K % C % C % C % C % C % C % C % C % C       Cotton 0 30 100 0 20 60 100 0 0 20 0 100 70 95 20 0 100 100 100 100     100 80 100 30 90 100 80 100 Soybean 0 40 0 20 20 60 100 0 0 0 0 100 0 0     0 0 100 100 100 70 90 100 80 40 60 90 90 70 Field Corn 0 30 30 0 0 70     100 0 0 0 0 100 30 0 30 30 100 100 100 100 70 100 90 0 90 70 100 100     Wheat 0 30 50 10 20 20 100 0 0 0 0 100 0 0 0 0 100 100 100 100 20 90 80     40 100 100 40 100 Field Bindweed 0 40 100 0 0 30 100 0 0 0 10 100 70 0     70 70 100 100 100 100 90 50 100 0 60 100 50 100 Morningglory 0 40 100 0     0 30 100 0 0 20 0 100 20 60 10 10 100 100 100 100 90 70 100 10 50 80 80     100 Velvetleaf 0 60 100 0 0 60 100 0 0 100 0 100 100 100 100 100 100 100     100 100 100 100 100 50 100 100 90 100 Barnyardgrass 0 0 30 30 0 20 100     100 0 0 0 100 0 20 20 20 100 100 100 100 100 100 100 30 90 100 100 100     Green Foxtail 0 20 100 0 0 100 100 -- 0 0 0 100 -- 100 100 100 100 100     100 100 100 100 100 100 100 100 100 100 Johnsongrass 0 0 100 0 0 40 100     100 0 0 10 100 90 60 100 100 100 100 100 100 30 100 100 30 90 100 70     100   Compound No. 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47     48 49 50 53 55 73 75 76 77 78 Rate (kg/ha) 8.0 8.0 8.0 8.0 8.0 8.0 8.0     8.0 8.0 8.0 8.0 0.5 1.0 1.0 0.5 4.0 4.0 4.0 0.25 2.0 2.0 0.25 0.5 4.0     1.0 1.0 4.0 1.0 Species % C % C % C % C % C % C % C % C % C % C % C % C     % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C       Cotton 100 10 10 10 20 90 90 0 10 30 60 100 100 100 100 100 10 90 50     100 80 90 40 80 100 90 100 100 Soybean 90 20 10 30 10 80 90 0 10 40 60     70 100 90 100 90 10 90 30 100 50 80 30 50 100 90 90 60 Field Corn 100 20     20 20 20 10 90 0 20 30 30 80 70 80 100 100 0 10 0 100 100 90 10 40 80 40     80 20 Wheat 80 20 10 20 20 30 30 0 10 30 30 70 100 20 100 100 0 10 0 10     70 40 20 80 70 30 50 40 Field Bindweed 100 0 10 20 10 30 100 0 10 30 40     100 100 100 100 100 10 50 10 90 80 80 20 80 100 100 100 80 Morningglory     100 10 10 30 20 10 100 10 10 20 60 100 100 90 100 100 40 30 10 90 20 80     40 80 100 90 100 80 Velvetleaf 100 0 10 20 20 100 100 0 0 60 80 100 100     100 100 100 0 90 90 100 100 100 80 100 100 100 100 100 Barnyardgrass 100     30 20 20 30 30 80 0 10 40 30 80 100 100 100 100 10 0 0 100 90 90 10 20     80 30 100 50 Green Foxtail 100 20 10 20 10 80 100 50 30 70 90 100 100     100 100 100 50 90 20 100 100 100 30 90 100 80 100 50 Johnsongrass 100 30     20 20 20 30 80 0 0 50 50 90 100 60 100 100 20 0 0 50 90 60 0 80 80 50 80     40       Compound No. 82 85 86 89 96 113 114 119 124 125 182 183 184 185 186     187 188 189 190 191 192 193 194 195 196 197 198 200 Rate (kg/ha) 2.0 0.5     0.125 0.5 0.5 8.0 1.0 0.5 4.0 1.0 0.5 0.5 0.5 0.5 4.0 4.0 2.0 1.0 1.0     8.0 8.0 8.0 4.0 0.5 2.0 4.0 1.0 1.0 Species % C % C % C % C % C % C % C     % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C     % C % C % C       Cotton 95 95 95 80 100 0 100 70 100 100 100 80 90 30 30 30 30 80 80 80     90 100 100 70 90 90 100 100 Soybean 95 90 70 90 90 20 90 30 100 80 80 60     60 10 20 10 10 60 80 60 50 100 80 30 70 30 100 80 Field Corn 100 80 90     95 100 20 100 20 100 100 90 100 100 30 10 20 10 20 40 90 90 100 100 30     20 0 95 95 Wheat 90 50 70 80 90 10 50 10 100 90 80 30 70 10 10 20 20 20     20 50 50 100 40 30 0 0 100 90 Field Bindweed 100 95 95 70 100 10 100 70     100 100 100 30 80 10 20 0 30 30 50 30 30 100 90 50 60 0 100 100 Morninggl     ory 90 80 100 60 100 10 100 40 100 100 100 40 70 30 0 0 10 70 90 70 100     100 100 80 30 0 100 100 Velvetleaf 100 100 100 100 100 20 100 100 100     100 100 90 100 50 30 10 100 100 100 100 100 100 100 100 100 100 100 100     Barnyardgrass 100 70 90 90 100 20 100 30 100 100 100 10 50 10 20 0 10 20     80 90 100 100 90 90 90 30 100 100 Green Foxtail 100 100 100 90 100 10     100 40 100 100 100 90 100 30 0 0 20 40 90 90 100 100 80 100 100 70 100     100 Johnsongrass 80 60 30 90 90 10 70 30 100 80 100 30 80 0 0 0 0 20 30     80 100 100 30 80 0 80 100 95       Compound No. 201 202 206 207 208 209 210 211 212 213 214 215 218 219     220 221 222 223 224 225 226 227 228 229 230 231 232 233 234 Rate (kg/ha)     1.0 1.0 4.0 1.0 1.0 1.0 1.0 2.0 2.0 4.0 8.0 4.0 8.0 1.0 2.0 2.0 1.0 1.0     1.0 0.25 2.0 0.125 0.5 4.0 2.0 0.5 2.0 0.5 0.125 Species % C % C % C % C     % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C % C     % C % C % C % C % C % C % C       Cotton 95 100 90 100 100 100 50 100 100 100 30 100 70 95 80 95 95 100     100 100 100 90 100 90 100 40 100 95 70 Soybean 70 90 80 100 100 90 20 95     100 100 50 100 60 60 100 95 80 100 80 80 95 60 100 60 100 80 100 95 60     Field Corn 100 100 100 50 20 20 10 100 100 100 80 100 30 70 90 95 40 40     40 60 100 90 30 30 100 0 100 40 80 Wheat 70 40 40 90 90 30 20 100 100     100 30 100 10 50 40 50 30 95 40 60 100 90 80 50 100 50 100 80 70 Field     Bindweed 100 100 95 100 100 100 100 100 100 100 90 100 90 80 90 100 100     100 60 95 100 100 100 80 100 100 100 100 70 Morningglory 100 100 90 90     100 100 100 100 100 100 100 100 40 90 100 100 95 100 50 90 100 95 100     100 100 100 100 80 80 Velvetleaf 100 100 100 100 100 100 100 100 100 100     100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 95     100 Barnyardgrass 95 100 95 100 100 100 95 100 100 100 60 100 0 70 100     100 0 100 10 60 100 100 100 90 100 20 100 100 80 Green Foxtail 100 100     100 100 100 100 95 100 100 100 95 100 90 95 100 100 60 100 40 90 100 100     95 95 100 40 100 100 95 Johnsongrass 40 80 100 80 70 70 60 100 100 100     80 100 0 30 50 100 0 100 10 40 100 95 95 70 95 10 100 30 40

I claim:
 1. The compound of the formula ##STR62## wherein R¹⁵ is analkyl group of 1 to 4 carbons; X¹ is fluorine;X² is chlorine or bromine;Z is fluorine, chlorine, bromine, iodine, nitro, amino,alkoxycarbonylamino of 1 to 6 alkyl carbon atoms, di(alkylcarbonyl)aminoin which each alkyl is of 1 to 6 carbon atoms, hydroxysulfonyl,halosulfonyl, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 5 carbonatoms, --QR, --S(O)_(m) R⁸, --Q² R⁹, Q is O R is hydrogen, alkyl of 1 to6 carbon atoms (which is unsubstituted or substituted with cycloalkyl of3 to 7 carbon atoms), cycloalkyl of 3 to 7 carbon atoms (which isunsubstituted or substituted with alkyl of 1 to 6 carbon atoms), benzyl,alkoxyalkyl of 2 to 8 carbon atoms, alkoxyalkoxyalkyl of 3 to 8 carbonatoms, alkylthioalkyl, alkylsulfinylalkyl, or alkylsulfonylalkyl of 2 to8 carbon atoms, alkyenyl or haloalkenyl of 2 to 5 carbon atoms, alkynylor haloalkynyl of 2 to 5 carbon atoms, haloalkyl of 1 to 5 carbon atoms,alkylcarbonyl of 1 to 6 alkyl carbon atoms, or dialkylaminocarbonyl ordialkylaminothiocarbonyl in which each alkyl is of 1 to 6 carbon atoms.2. The compound of claim 1 wherein R¹⁵ is alkyl of 1 to 4 carbon atomsand Z is fluorine, chlorine, bromine, iodine, nitro, amino,hydroxysulfonyl, chlorosulfonyl, or a group --OR in which R is alkyl of1 to 6 carbon atoms, benzyl, alkoxyalkyl of 2 to 4 carbon atoms, oralkenyl or alkynyl of 2 to 5 carbon atoms.
 3. The compound of claim 2wherein Z is nitro, or the group --OR.
 4. The compound of claim 3wherein Z is the group --OR and R is alkyl of 1 to 4 carbon atoms.